In this lecture, we will discuss catalytic metathesis. Metathesis, as we had discussed in the last lecture, it is a change in place. In the case of olefins, when you have alkylidine groups and if alkylidine groups change places, then you would have a metathesis reaction. In the slide that is there before you, you will notice that two alkenes and they are the same alkene A B, which is basically indicative of two alkylidine groups joined together. If we do a metathesis of this A B olefin, then you can get both A A and B B. If you remember this allows for a change in the size of the olefin.  This is very useful for the petroleum industry. In fact, metathesis was originally discovered in the industry and eventually it was understood better through the work of Chauvin. He discovered what is called the non pair wise mechanism for the metathesis. We will just briefly revise what we have discussed earlier. I have before me a set of four olefins, which are represented by these green, magenta, blue and black alkylidine groups. The alkylidine groups that are going to be exchanged are the ones which are shown in round as a round figure. The alkylidine groups which are stationary or will remain in the same place are the ones which are in square shape. So, you will notice that if you take four different olefins, you can have a complete random distribution of these olefins. The gray round figure which is attached to the metal which is basically having M double bond CH2 here is going to be exchanged with the green one to start with. Then the green alkylidine group is exchanged with the magenta and the magenta is exchanged with the one in the transposition. So, you will notice that the round magenta has gone here. The green one has come here and the blue which was here has come over to this position. So, this is just to indicate that you can have a completely random distribution of the alkylidine groups. This non-pairwise mechanism was suggested by Chauvin and you will recollect that Chauvin got the Nobel prize in 2005 for this very reason for discovering the actual mechanism that was behind this famous metathesis reaction. Pictured here is the mechanism. You start with M CH2 M double bond CH2 and then you can exchange it with another olefin in such a way that you can eliminate ethylene. That is what is happening here. Ethylene is eliminated and a new alkylidine metal system is generated which can interchange with another alkylidine group of another olefin in order to finally generate a completely new olefin. So, these are the two products. This is product 1 and this is product 2 and these two olefins are generated starting with two olefins which is the reactant 1 and reactant 2. This is reactant 1 and this is reactant 2. So, based on this type of a non-pairwise mechanism it was possible to explain all the reactions that were observed in the metathesis reaction. So, what we have not discussed in the last lecture where we discussed the mechanism of this process is a fact that the catalyst required for metathesis were often very complex. Originally it was discovered by a standard oil company and patented also by Philips petroleum for a specific case. Most of these companies used very complex mixtures for carrying out metathesis. In general it could be said that early high oxidation state metal ion or a metal complex an oxide or a chloride was used and this was followed by a reducing agent. So, a high oxidation state metal. So, this is the high oxidation state metal that I am talking about and then this was combined with a reducing agent. Very often this was an aluminum alkyl species aluminum alkyl or aluminum alkyl chloride and then surprisingly small amounts of ethanol or water were required in order to initiate the reaction. There were several disadvantages for this particular mixture. One was a fact that the catalytic species was not known. It could be a variety of different species which were generated starting from this mixture. So, the catalytic species itself could not be modified. It was an unknown species and there was very often an initiation period that was required in order to start the reaction. So, the reactions were slow to begin with before they took off. This means that the reaction itself would lead to in terms of when you have reactions which lead to polymers, you have a large range in the molecular weight. We will talk about this a little later on during the course of this lecture also. So, this is a big disadvantage, but nevertheless the petroleum companies found it extremely useful to do metathesis reaction in order to generate more useful fractions from the petroleum fractions that were isolated directly from the crude that were isolated from the crude. So, it was a useful reaction, but then the catalyst was not known. After Chauvin unraveled the mechanism of the reaction, it was clear that one needed a carbene. So, this carbene catalyst was used or was one of the first ones which was rationally designed. You will notice that this species, this carbene species was the catalyst, but it was still in a high oxidation state. It required an aluminum alkyl species, aluminum halide in order to activate the species. So, Lewis acid was apparently for some reason it was required in order to carry out this reaction forward. This Lewis acid activation is presumably to generate a vacant coordination site on the tungsten. So, this was better than complex mixtures. The complex mixtures that were originally known for carrying out metathesis reactions were extremely complex. This was better. It was too component, but still it was not as good as what one would desire. So, the first breakthrough came from the work of Schrock and Grubb. We will discuss these two in detail. We will take up the Grubb's catalyst first and then we will talk about the Schrock's catalyst. Grubb's catalyst was a modification of the carbene systems that were known which were derived from fissure carbene. Fissure carbene were those species where you had a late transition metal along with a carbon bearing a heteroatom. However, when you replace the heteroatom with all alkyl groups, the carbene became lot more reactive and especially reactive towards the metathesis reaction itself. So, this catalyst which was first made by Grubb's which is called the first generation catalyst from the Grubb's group is extremely important for several reasons. First of all, it was the first single component catalyst which means that it did not require another species in order to initiate the reaction. Secondly, it was the precursor for several other second generation and third generation Grubb's catalyst. This is also important and the fact that it could be easily generated and the reaction that is used for making this complex is shown here. In fact, R U C L 2 P P H 3 thrice is the starting material and this starting material can now be reacted with a diazo carbene precursor. This leads to transfer of the carbene to the ruthenium and this molecule is a stable molecule which can be isolated and characterized. This species which is generated by attaching a carbene to the R U C L 2 P P H 3 thrice turns out to be less reactive. It is not as good a metathesis catalyst, but when you replace the tri phenyl phosphine with tri cyclohexyl phosphine with a simple substitution reaction, you end up with the first generation catalyst. This is the first generation catalyst from the Grubb's group and it turns out to be a good metathesis catalyst. So, there are advantages for this catalyst system. First of all, it can be readily synthesized very easily synthesized in the laboratory. It is a stable system which can be stored and used again and again without difficulty. You do not have to make it fresh every time you want to do the reaction. So, this is the primary advantage and it is a single component catalyst. As I said, that is the major advantage of the Grubb's catalyst. Now, after Grubb's declared the synthesis of this catalyst, it turns out that several people wanted to make better metathesis catalyst. Something that would be more reactive than the first generation catalyst which could not be used with several substrates. Three people, Nolan, Grubb's and Fusner, discovered that if you can attach n-heterocyclic carbene. This is a n-heterocyclic carbene which we have encountered earlier. If we can attach n-heterocyclic carbene to the ruthenium replacing one tricyclohexyl phosphine on the ruthenium with a carbene, then the catalyst turns out to be much more reactive, much more useful and presumably the electron density on the ruthenium is increased. It is also true that you have large aryl groups which protect the ruthenium center from unnecessary reactions and decomposition. Now, all three of them published this about the same time, but following this initial result Grubb's showed that if you replace the unsaturated n-heterocyclic carbene in the present system, you have an unsaturated heterocyclic carbene. If you replace it with the saturated variety of n-heterocyclic carbene, then it turns out that the reaction is much much better. The variety that Grubb's made actually had simple methyl groups to protect the aryl to give steric protection to the ruthenium and you have a stable ruthenium complex. In fact, you for the sake of our understanding, we will convert that single bond into a double bond because we normally talk of this as a carbene and the carbene coordination to the ruthenium is the one that promotes the reactivity of this center. During the course of this reaction, it is usually P C Y 3 which leaves and generates a vacant coordination site on the ruthenium. In general, if you want a catalyst to function, in the resting state you would have a ligand, an extra ligand which leaves and generates a vacant coordination site which initiates the reaction. Grubb's published the synthesis of this compound and its reactivity just a few months after he had published the unsaturated variety, but it was very clear that the unsaturated variety was the most active form. So, it became what was called popularly as a second generation Grubb's catalyst. The second generation Grubb's catalyst turns out to be a lot more reactive, stable and useful for carrying out metathesis reactions. Now, during the course of this study, if there were other attempts to modify the N-heterocyclic carbene in such a way that it would give you a system which would generate a very reactive catalyst and this time mentioned should be made above the Hovayda Grubb's catalyst. This was a combination of the Grubb's catalyst system. Basically you had an N-heterocyclic carbene which was a saturated variety and you also had a carbene which was the essential reactive component of the metathesis catalyst, but the P C Y 3 was replaced with a pendant group on the alkylidine such that it coordinated to the ruthenium and blocked that site. So, the vacant coordination site at the ruthenium was very readily generated by loss of this R U O bond. So, this R U O bond was lost initially and that led to a reactive form of the catalyst. Now, this turns out to be a little more useful it is less reactive, but it is more stable because of the internal coordination of the alkylidine. So, when you design a catalyst, it is very important that you design a catalyst that is as reactive as possible, but at the same time it has a long shelf life and that is what we consider by more stability. However, these two things are very often working at cross purposes because if you make the complex very stable then it will be less reactive. So, let us proceed further after Hoverida made this modification for the Grubb's catalyst. The Grubb's second generation catalyst was the one which was most useful, but it was not very reactive. Grubb's showed that if you replace the pendant group with a pyridine unit, a substituted pyridine and if you react the Grubb's second generation catalyst with pyridine, specifically broma pyridine then it turned out to be an extremely useful catalyst. It was extremely reactive. In fact, it initiates metathesis a million times faster than the second generation catalyst. This like I said earlier, it turns out to be an extremely important fact for polymerization. If you do polymerization, metathesis polymerization, which we will talk about in a few minutes, if you do metathesis polymerization and if there is a long initiation time for the catalyst to start functioning, then you will end up with polymers with a variety polydispersity which is undesirable. So, it is important to have as low a polydispersity as possible. That means the molecular weight range is very small. Then you get much better polymers with better physical characteristics. So, it is important to have a catalyst which is extremely fast, which has no lag time for the initiation of the reaction. So, this catalyst which is called the third generation catalyst is an extremely fast catalyst, which initiates metathesis a million times faster than the second generation catalyst. Now, let us take a look at Schrock's design. Schrock was a person who was working with early transition metals and high oxidation state carbene compounds. If you remember, the metathesis catalysts that were initially designed, that were known in the patents, were all early transition metals oxides or chlorides, which were activated with an alkylating agent. Either a tin or R 4 tin compound or it was an AL R 3 compound, something that would alkylate early transition metal. So, Schrock's design is quite natural. It starts with a molybdenum species, which is there in the high oxidation state. He showed that if you take a carbene, a Schrock carbene, which surprisingly has no hetero atom to stabilize it. If you take the Schrock carbene and if you attach to alkoxide units, then it can function as a metathesis catalyst. But surprisingly, the alkoxy groups which are attached to the metal have to bear some electron withdrawing groups. If they are not electron withdrawing, then they are not as reactive as one would like them to be. So, the Schrock's catalyst, the most celebrated form of the Schrock's catalyst is what I have shown here. This has got two trifluoromethyl groups attached to the tertiary butyl, tertiary butoxy unit that is attached to the molybdenum. This is a Schrock's catalyst, which turns out to be the most useful form of the catalyst. It has got an alkylidine group. So, M double bond CH2 is still the basic unit, which is the catalytically active unit for metathesis. That remains common for both Grubbs's catalyst and Schrock's catalyst. The only difference is the fact that the molybdenum catalyst that is the basis for the Schrock's catalyst has got two alkoxy groups, which are electron withdrawing in nature. Now, Schrock's catalyst also had another advantage and that advantage is shown here. That is the fact that you can generate a chiral Schrock's catalyst. Now, if you remember, the catalyst center has got two alkoxy units and binol, which has got an axially chiral molecule, which means that there is no single carbon, which bears a asymmetric unit. The chirality comes from the fact that you cannot rotate these molecules around this carbon-carbon bond very easily. So, the chirality resides in the fact that these two planar rings are oriented in such a way that they have a helical axis to them. So, now you have two alkoxy groups. This is the binol unit, which is attached to the molybdenum and it bears a chirality at the molybdenum. Now, if you can do a catalysis using this alkylidine unit, the molybdenum center, which is carrying out metathesis always has a chiral center. So, whenever you have the possibility for generating some stereo selective carbon-carbon bond formation, then it would be possible to do it in a selective way when you have this chirality or this handedness on the molybdenum center. So, the grubbs catalyst at the moment at least the ones that I have shown you do not have the chirality inbuilt in them. Whereas, the Schrock's chiral catalyst has this major advantage in that there is a chiral center, which is attached to the molybdenum and which is retained right through the reaction. So, it turns out to be an extremely useful center for inducing chirality. So, let us see how these systems are being used. So, we have discussed the catalyst in detail, but in all the cases it is only the M double bond CH2 that is really important for carrying out the reaction. So, it is only the M double bond CH2 that is a catalytically active center and whatever we have described, the rest of the paraphernalia that is attached to the metal purely provides assistance in terms of stabilizing the molecule, stabilizing the catalyst or providing the right electronic input into the metal so that the catalysis can be carried out. So, let us go to the actual examples where reactions can be carried out. I would call self-metathesis as a first example. Suppose you just have two alkali-dene groups which are identical and you carry out metathesis, you would end up with reactants and products which are the same. I would call this self-metathesis and there is no thermodynamic loss again in this whole process and there is no effective reaction also. So, it is not of great utility to have the self-metathesis. So, the more useful reaction is the one where you have cross metathesis. Now, let us imagine the extreme scenario where you have four different alkali-dene groups attached to the olefin. So, in other words two olefins are undergoing metathesis and there are four different alkali-dene groups. I have labeled them as A, B, C, D which means A is one alkali-dene group B is a different alkali-dene group. Similarly, C D is a different olefin. Now, you just imagine the metathesis reaction carried out in this case will lead to almost 10 different olefins because the alkali-dene groups unless they have very strong electron withdrawing or donor groups on them, you will not have a major difference in the delta H of this reaction goes from left to right after metathesis. So, if you have A A, B A B, A C and A D, they are four different olefins that can be generated starting with the alkali-dene group which is A attached to the alkene and then it is transferred to the metal and then it can be transferred to any one of the other olefins. Similarly, you can write out the remaining number of olefins that can be generated with each one of these alkali-denes and you will realize that there are 10 of them. So, 10 different alkenes can be generated. In the event that the alkali-dene is symmetrical, you will have only 10. If you have an unsymmetrical alkali-dene group which means that you have let us say C H 3 C H group. So, if the alkali-dene for example, has got this type, this is the alkali-dene group that we are talking about, then you can have both cis and trans olefins generated from this alkali-dene. So, a maximum of 20 alkenes can be generated just starting with two alkenes and four alkali-dene groups. This is the maximum that can be generated starting with four different alkali-dene groups. So, now let us take a look at how one can utilize such a reaction which leads to a complex mixture of 10 alkenes or 20 stereoisomers. How can that be of any use? So, this is something that we need to consider. Very often the cross metathesis reaction which is what we are talking about when you have different alkali-dene groups is designed in such a way that it will give us only the product which is of importance and the other product is conveniently eliminated from the reaction mixture either because it is volatile or in such a way that it can be isolated very easily. So, let us take a look at this reaction which I have indicated here whether it is cis or trans alkene if you can combine it with ethylene let us say and carry out a metathesis reaction. I have indicated the metathesis catalyst as alkali-dene as a carbene metal carbene unit. In principle it can be either a shock catalyst or a grubbs catalyst, but in this in the case of olefins very often it is convenient to just take the more readily available and less air sensitive grubbs catalyst and carry out the reaction and one will end up with these two alkenes during the course of this reaction. If you want to control this reaction in such a way that I want to make only the alkali-dene only the alkene which is pictured here I can push this reaction to the left very simply by allowing the ethylene to escape from the reaction mixture. So, the Lysiatelius principle will be operating and one would go from the right side of this reaction to the left side and ethylene would be allowed to escape. Suppose I want to split a very large olefin which has got say C 18 olefin which has got the double bond in the middle and I want to convert it into two olefins which are smaller in size then I can just have a high pressure of olefin. So, if I control the concentration of ethylene I can move the reaction from left to right. If I increase the ethylene concentration I can very simply make the smaller olefins and move the reaction from left to right. So, this turns out to be a useful way of controlling the metathesis using the Lysiatelius principle. It is also known that there are some electronic factors which control the reaction. Here I have shown an example where I have an electron withdrawing group on the olefin in which case then the reaction turns out to be useful if I have more amount of this electron withdrawing group attached to olefin which is marked as this aldehyde the substituted butyl aldehyde here and that is taken in a slightly larger amount. You will notice that this can again end up with elimination of the two CH 2 groups and ethylene is eliminated during the course of this reaction and very conveniently you have generated a useful aldehyde which is now having a much larger molecular weight. And you will also notice that although you had an unsymmetrical alkylidine group. So, in other words this alkylidine could end up with both cis and trans you will notice that this reaction mixture ended up with the e by z ratio that means the trans compound the trans product was formed in a ratio of 20 is to 1 for the cis compound. So, this turns out to be a very easy way of generating starting with here I have shown this reaction was done with the Grubbs second generation catalyst and you ended up with a 92 percent yield just by adding two equivalents of the aldehyde that you started out with and you ended up with an aldehyde which is more useful and in 92 percent yield. So, this was carried out with Grubbs second generation catalyst and it allows for a reaction where you have an aldehyde as a substituent. Now, a similar reaction with a modified Grubbs second generation catalyst here again you get an silil substituted alkene and this can also proceed from one side to the other side purely by removal of ethylene from the reaction mixture and you end up with as 81 percent yield of the desired product and a e by z ratio of 11. So, in all these cases ethylene the amount of ethylene that was used was a amount of ethylene that was removed from the reaction mixture was key for pushing the reaction from left to right and generating the product that was useful. So, here I have shown you another example where you ended up with a useful product 80 percent yield again with Grubbs first generation catalyst is only 5 mole percent of the first generation catalyst very mild conditions you can convert the compound which is of use in this particular case it is the side product is a product that is reasonably volatile and can be removed from the reaction mixture. So, you can see that least at least principle is a key for generating useful products. So, you can also have some steric effects during the course of this reaction. Now, you will remember that olefins have a tendency to coordinate to metal atoms to a lesser extent when they are substituted. So, since the olefin has to be coordinated to the metal during the course of the reaction the reaction works well when you have less substituted olefins. Here I have shown you the first step in the whole metathesis process and that is the formation of the elimination of the alkylidine group which is attached to the ruthenium center on reaction with the starting material. So, here I have biased the reaction in such a way that I end up with only the substitution initial substitution of the alkylidine group on the ruthenium. So, if you look at the rates of these reactions at the rate at which the reaction proceeds this reaction proceeds from left to right you notice that if I have a single substituent on the ethylene so that is the fastest that proceeds at the rate of say 100 arbitrary units then the moment you have 2 substituents on the olefin in a cis position then the reaction slows down by almost 10 orders of 1 order of magnitude it comes down to 10 relative units. And similarly if you have a heavily substituted alkene and if you have a trans substituted alkene then the reaction falls by another factor of 2. So, you can see how the reaction goes slower and slower as you have greater and greater number of substituents and the cis substituent is substitution pattern is better than the trans substitution pattern. And this turns out that if you have a heavily substituted olefin especially one with a phenyl group so if you have a styrene then the reaction is practically virtually non-existent with when you have the grubs first generation catalyst. So, this gives you an idea about how it is important to have very reactive olefins and if you want to carry out the reaction in a fast manner. So, there are various ways which allow you to control the reaction and these are used very effectively for doing cross metathesis. Now, we come to a special class of reaction which is called ring closing metathesis reaction. The ring closing metathesis reaction is a special case when the two olefins which are undergoing metathesis belong to the same molecule. So, if I have two double bonds which are positioned in such a way that you can eliminate two alkaline groups and form a ring. So, basically what we are doing in this particular case is we are eliminating these two CH2 groups we are eliminating these two CH2 groups and forming ethylene. And as I told you earlier elimination of ethylene is very often a convenient way of pushing the reaction from one direction to the other direction. So, this itself drives this because ethylene is a volatile species which can be eliminated from the reaction mixture. More than that the reaction is entropically favored by having the two groups which are joining together form a single molecule. So, in other words two different olefins are not formed a single olefin is formed and that leads to a five membered ring which is entropically very favorable. This is a five membered ring which is formed and the new bond that is formed in between these two carbons turns out to be a very favorable situation. So, Grubbs first generation catalyst is convenient for carrying out these type of reactions. And you will notice that E is actually a electron withdrawing group and very often it is it is C O O E T or C O O M E. And this you will recognize as a species which is coming from a dialkylation of diethyl malanate. So, if you take CH2 C O O M E C O O M E di methyl malanate and you alkylate this active carbon then you will end up with this particular starting material. And it is a very convenient starting material and you can generate this five membered ring very readily using a ring closing metathesis reaction. This turns out to be useful and it can even be done with larger size ring not necessarily with a five membered ring. And once again Le Chatelier's principle is utilized so that you can remove ethylene and form a very nice ring system. Let us take a look at the mechanism of the ring closing metathesis. Why is it that it is so convenient to carry out the metathesis reaction? I have color coded the alkylidine group which is present on the ruthenium to start with. And you will notice that the replacement of this P C Y 3 on the ruthenium with the olefin from the starting material or the reactant led to a ruthenium alkylidine alkene complex. This is a key intermediate. Now, starting with a ruthenium 2 center you end up with formally a ruthenium 4 center. Here you carried out what we call as a oxidative coupling reaction where the ruthenium undergoes formal oxidation. And you have coupled two carbon centers basically the two carbon centers which are coupled are marked here in the dotted lines and so you end up with a new bond which is a metallocyclobutane a ruthenium metallocyclobutane is formed. And this ruthenium metallocyclobutane can now break in a different fashion. Earlier you had the formation of you had the formation of a new carbon carbon bond between this CH 2 group which was coming from this starting material. And the alkylidine alkylidine group which is present on the metal. Now, I can eliminate this alkene I can eliminate this alkene and I shall show it in a different color. So, that you can follow it very easily I break these two bonds and form a new carbon carbon double bond. If I form a new carbon carbon double bond then I end up with this product is eliminated. And I have an alkali alkylidine group where the starting material is now coordinated to the ruthenium. I have an alkylidine group which can now carry out another metathesis reaction. Now, with this olefin which is attached to the same molecule. So, an alkylidine group which has got an alkene inside as an internal reactant turns out to be a very fast reaction. And that is what we have written here. Now, we move this CH 2 double bond to this position. If you move it to this position then you end up with a cyclic intermediate and the cyclic intermediate once again forms a bond. This time the ruthenium carbon bond is formed here and the carbon carbon bond is formed here. The new carbon carbon bond the metal now again goes from plus 2 to plus 4 oxidation state. And this can now eliminate can break in such a way that you form R U CH 2 as a final as a catalyst again as a regenerated catalyst and the cyclic product which is listed here. So, we can write these two systems together. Now, I will start with the R U CH 2 which I generated in the previous reactant step. Now, we can go through the catalytic cycle fast. You have the formation of a metallic cyclobutane which is listed here. And it can eliminate cyclo pentene which regenerates the catalytically active intermediate. So, this is the mechanism of the ring closing metathesis. This is the mechanism of the ring closing metathesis. Now, you will notice that the same reaction can be pushed in the opposite direction if you have a large amount of ethylene. Suppose, I have a high concentration of ethylene. If I have a high concentration of ethylene and I take the ring closed product then I can have a ring opening metathesis. So, this is called ROM. The previous one is called RCM and this one is called ROM ROM and the ring opening metathesis can push the reaction from the ring closed system to the ring open system. Now, exactly the same reaction can go back. The same steps can be retraced in order to generate this product. In this particular instance, this is the product. So, you can realize how the reaction can be used to very effectively go from one direction to the other direction in a very effective fashion to generate a wide variety of static materials and products. So, once again I can take the reactant which I had shown you earlier which is the diethyl malonate which has been alkylated, dialkylated using two allyl groups. That again is an easy step. If I take these two diallylated species, I can in fact eliminate ethylene once again. From two different molecules, now that will lead to a new diene. This time it will be actually a triene. It is a triene because you have generated a new double bond in the process. So, two dienes come together and form a triene. Now, you will realize that you can keep adding these molecules together in such a fashion that you can form a polymer. So, I can remove two CH2 units from one of these molecules and another one of the starting material and lead to a polymer. So, this is a polymerization reaction which is executed through metathesis. In each step, ethylene is eliminated and because ethylene is a volatile molecule that can be quickly removed from the reaction mixture and you can have a very efficient way of polymerizing diene. So, this is called acyclic diene metathesis polymerization. Acyclic diene metathesis polymerization is a system where you eliminate ethylene from a diene molecule in such a way that you form a polymeric molecule. How do you push the reaction? The same reactant has been used for three different reasons. One is to do ring opening metathesis, another is to do ring closing metathesis, another is to do acyclic diene metathesis polymerization. So, here the concentration of the diene is a key. Concentration of the diene if it is very high, then the polymerization results and if you remove ethylene during the process, then you can very effectively make a large high molecular weight polymer starting with an acyclic diene. If you add a lot of ethylene to a cyclized product, then of course, you can go from the ring closed product to the ring open product. So, you can push the reaction in different directions based on the concentration of the reactant which is there. Polymerization is a competing process whenever you do ring closing metathesis polymerization or a ring opening metathesis polymerization. So, the lower concentration always prevents polymerization. If you have a large amount of the diene, large concentration of the diene, then the possibility of the diene reacting with itself is higher and that of course, leads to polymerization. If you have high temperature, then the ring opening and the elimination of ethylene is promoted because delta S t, delta S increases in the process and you can have larger free energy change, negative free energy change. As a result of the reaction, so that would be a more favorable process when you have the reaction proceeding in a forward direction. That means you have ring closing during the whole system. If you remove ethylene, of course, you want to do ring closing reaction. You should remove ethylene from the reaction mixture, so that it does not come back and compete for the reaction. So, you can see that how this particular metathesis reaction is extremely useful and it has been used extensively for the synthesis of a variety of natural products. The natural product synthesis, especially for unusual ring systems, has been conveniently accomplished using the metathesis catalysis. Here, Schrock, the Schrock catalyst has been used very effectively. You have two reactive groups. You have an amide functionality which is present here and you have a ether functionality and in the presence of these functionalities, if you want to do a metathesis reaction, it is convenient to do it with the Schrock catalyst. The Schrock catalyst carries out this whole reaction in 95 percent, in 98 percent yield and if you, but you need a large amount of the catalyst for this whole process to function. Nevertheless, this is a very efficient way of making such a large ring natural product and very effectively you can generate the ring system and a ring recent synthesis of another natural product, manzamine, manzamine A which has been isolated from a marine organism is shown here. This was accomplished by a ring closing metathesis in the presence of very labile functional groups. This is a very complex natural product with so many ring systems and in spite of all that, the reaction could be carried out and Fukuyama and co-workers have recently published the total synthesis of such a complex natural product. The last step is the ring closing metathesis which was accomplished which led to the generation of this chiral natural product being synthesized very efficiently. So, with this I would like to end today's lecture. I will show you some of the key options. So, we will summarize today's lecture by saying that metathesis requires a carbene complex. It can also be carried out with a carbene complex with acetylenes. We have not discussed this in today's lecture, but it is also possible. The most important point to note is the fact that there is non-pairwise exchange. This non-pairwise exchange means that you will have a plethora of products in this whole reaction. In order to carry out this reaction effectively, you need to utilize thermodynamics to the health. So, if you have to use Lysiatoly's principle, that is the most important principle that can be used to advantage. In order to push the reaction in the direction in which you want to carry out the whole push the reaction from the reactant to the product side, you have to utilize Lysiatoly's principle very effectively. Temperature and concentration also are important when you have to carry out polymerization reactions. You can utilize the whole thing with efficiently when you use high temperatures and T delta S is large. So, you can push the reaction to the side in which you want to carry out the reaction efficiently. So, the metathesis reaction, although it seems to be such a non-specific reaction, it generates a large number of products very easily. You can use it very effectively if you remember that the importance of, if you remember the importance of thermodynamics, you can push it in the direction in which you want to proceed. So, in the case of carbines, you can use the reaction with acetylenes and you can generate metathesis of carbines and that leads to acetylenes, polyacetylenes which are very difficult to make otherwise and you can make very interesting materials which we shall cover in a future talk.


What's happening, man?  I was a big Mike Tyson's fan.  Oh, man. I'm telling y'all, I was nice with that. I got to the point, I could put Mike down and win, I think, the second round. Because I don't think you can actually knock him out in the first one, no matter what you do. But I was nice. So let's see the Mayweather. It's a punch out.  You gotta agree to his terms, down Flamenco's body. Back to him, too. You do like one punch, didn't you? That was it. All right, y'all. Post your comments down below. Let me know what you think. If you enjoyed my reaction, hit the like button, share, and subscribe. If you didn't, you probably love Mayweather. One million subscribers. Woo!


Good morning, cyber traders. Welcome. Happy Monday on this 11th of February. How's everybody doing? Good to see you, Mark. There you go Sonny, good to see you. Nice talking to you on Friday. Lita, good to see you. Ken, everybody All right. It looks like everyone's doing fine Bob, good to see you. George, Lewis. All right. Good. Good. All right, everybody. So, well, it's a brand new week So with a brand new week, there's always uh A lot of it's a whole new adventure. So listen, whatever happened last week Some of you guys did great. Some of you guys broke even some of you guys still learning and do too well But remember every day is a new adventure, uh, especially when you're starting a brand new week So, uh, let me see what's going on. There we go. Hopefully that's not playing anymore all right, so Let's uh, just remember everybody today is your typical monday and you know I didn't hear that much big news over the weekend I mean, I mean a big thing is you see a lot of political things stuff going on But I don't I didn't see a lot of things that affect the stock market as much Uh, you did hear that the democrats came out with this whole new green deal thing. So, um, Which sounds pretty interesting, which probably would affect some of the Some of certain stocks. I see some of the ETFs like gas stocks are I don't know if that has anything to do with it, but uh, I would keep an eye on stocks like tesla and uh NiO, you know any of those solar or uh, you know electric cars, you know, that might make a big big run But let's just see what happens becomes fruition. It doesn't doesn't matter a point is, you know Remember wall the same party and the party is the training party. So always remember that So whenever these people come out with something if it's the new border wall whoever's building it remember with steel We did pretty well on that one when uh, president trump was coming out praising steel We did pretty well on that but they were all really good short-term plays So just take it well with a grain of salt now. There are a couple of stocks I do want to point out that are making there are making some serious news If I just want to really start off talking with the ea now a lot of you guys remember We looked at ea last week and the stock got crushed went from 95 open up at um, like 75 was down like 20 points Well, apparently whatever the news was was obviously false or somebody misinterpreted it. It must have been extremely positive But this stock had a great run on friday You can see how it ran from 86 all the way to 96 and it's pushing pretty damn strong right now Unfortunately for this stock right here for some of us it is expensive You know, we're not the fan of expensive stocks out there Several reasons why you can't see the good matrix iceberg orders out there. You can't see the uh, you know You need a lot more money to trade it, you know Why do it but listen there are some of you here that can afford it You know and Listen, there's 25 000 stocks out there We only want to trade the ones that have the most action and this one's got a nice little push So if you are in in the level four or level five category of a cyber trader, this is definitely right up your alley now um L we've been looking at this otl K trade right here. This is one that we found this morning. I don't know what the hell way this came from This thing just went from a buck all the way to 230 and just came straight down I don't know if that's a short squeeze or whatever, but that thing just I don't know How a thing like that ran that much In the pre market and then just tanked so you could see it just like a big big spike and came right back down Listen 1.6 million shares traded. Um, you know, I'm not a fan trading stocks under a dollar But uh, it finally broke a dollar and the reason for it you got those uh, because then you deal with tens of a penny But over here you got great iceberg orders out there. You got great volume is exactly what we're looking for not the most, you know Attractive stock to trade in pre market, but we'll put it on the watch list something a little bit better And everybody knows this one if you're a cyber trader student Remember we trade this stock about a couple of weeks ago. It ran from five all the way to about 14 dollars in one day This is one of about 300 percent movers right there now while i'm looking at it.  Remember we taught you in class, you know You do your journals for not just to remind yourself of things not to do But you do want to remind yourself because these stocks eventually will come back in play And you want to know how you traded it and you want to know exactly You know, was there a lot of shakes that it was it was a tradeable. What level was it at? And it's got great great great orders out here on the matrix. So you got great level three quotes Um, you know, she started building a pendant right here But because we know we traded in the past definitely put on a watch list It's not really right now the best looking stock As in, you know, with a good push on it, but we just know this stock does move very well I can't get shares to short avco Um mark, first of all, you don't short stocks that are going up.   All right Don't try to don't try to second guess it until you get better at it and you understand what's going on Listen, I know this stock's a big short squeezes But this stock goes from if you short the stock goes from five back to 13 you're done, you know, remember slow and steady another one, um A couple other ones, uh, nigl Came up my radar right here I'm sorry, uh The pcg PCg has been a pretty decent swing trade for us guys. You could see right here gorgeous falstil flag right there a lot of us, uh You know did pretty well on this big catastrophe and unfortunately their catastrophe is cyber trading cyber traders Uh opportunity gorgeous gorgeous falstil flag right there So it's not been a great swing a day trade, but you know what the stock is a swing trade Uh, I mean I I went long and I wish I still had my a lot of my shares You know one of the problems about being a day trader is you become too conservative You know and people like what conservative. Yeah, you do come because you're always looking to take the money Always looking to take the money you never look at the big which is a good thing But uh, sometimes if you see something like this you might consider otherwise, but you know what if it didn't I know some of us sold the stock at 30 and it went down to 20s and went down to six so You know timing is everything And uh, you know, obviously you could see the big winner big runner up And this is the reason why you got to be careful with these etfs now this stock is you know I'm not a really big fan of trading etfs for the purpose of you got to be pretty advanced They move pretty quickly. I know a lot of people says oh, he's got volatility Yeah, but your thing is just because it's got volatility doesn't mean you know you could trade it I mean I get people always come up to me and I when I talk about like on my You know the uh the open house events that we do. Oh you guys use time in sales Oh, I can't use it because it moves too fast. Of course it moves too fast when you're looking at something That's not tradable. That's why when you go through the lessons the first Lesson here at cyber trade university when you're a student here the very first most important lesson Is the first team remember we teach you the three t's tradable Trend and trap the first t is not about the commission It's about could you even get the stock and remember there are different levels when you look at a stock and I think that's You know, that's the most expensive part of a trade. Remember you didn't make money You didn't make a single penny until you sell the stock You're already losing and you always got to keep that in mind now There were a couple other ones that I did see here, but I wasn't too big fans of them There was this na the nakd, you know, once again, you can see she's under a dollar. I'm not really, you know I don't want to trade something like that There was this one too also the unva, but she's breaking lower lows I mean she gapped up humongous on friday went from 50 to 64 if she's break breaking down She could be a short, but look at the look there's no orders out there So you kind of playing with a little bit of fire out there on the losers I was hoping to get a couple of shorts Rgse I mean look Just not really bringing up anything worth watching. All right, so um, listen, it's a typical monday This is what happens on a monday. You don't get the greatest lists of stocks, which is perfectly normal But usually the market opens up because I remember it's the weekend A lot of people didn't really look at anything over You don't really get that much news over the weekend unless if there's a weekend buyout Or you know somebody, you know came out to cure for cancer or something like that I don't know. I mean, but as of or something happened to politics, but nothing really is going on that much So now and nobody comes out with earnings on the weekend That I kind of explains it all so uh, so it's a decent list I mean probably a little bit bigger than normal two and three stocks this morning is pretty much normal So remember hump days of tuesdays wednesdays and thursdays, so that's where we get our biggest list So uh, but you should always know what it's like to be here Listen monday mornings when some market opens up, we'll find a new list We'll work through our percentage gainers and we'll work to get like a team anything. I'm missing. I did not call out Uh sc Nice push nice trend, you know Uh, the only problem is it had a really nice close, but it's not doing anything no volume nothing going on with it So, I mean the spread is tremendous. So I probably would say no car I mean it's up a little bit seven percent twenty thousand shares uh You know, maybe I mean it's testing resistance levels right here at highs I mean you could put on the watch list. I mean we could add it but Like I said, I remember I don't want to we don't want to get desperate. All right, Fernando All right guys, so um, listen, we'll be back at two thirty So We'll find a new list. So once again for we have a new lot a lot of new members that are starting today Just uh, we are gonna remember there's a trading room not a teaching room So kind of keep your questions. Uh, if you have any questions, you have several instructors in the room and you know and advisors So if you have any questions feel free to ask But uh, just what we always say just look listen and learn. All right guys. Good luck today. Happy trading And uh, we'll be doing our next audio broadcast To trade going into the afternoon. Good luck everyone and welcome back


So let's begin reading at verse 15. I'll read to verse 18. We'll get into our study, Matthew chapter 24 beginning at verse 15 reading to verse 18 Now we'll go into a prolonged introduction. I have to give to you layers of information in order for us to understand the context and so I'll read these verses then I'm going to give you a Long introduction I'm going to ask you to listen to me as I'm sharing with you to lay those layers in order that you'll get a better View of what is what is being spoken of here and in these verses so beginning in Matthew 24 at verse 15 therefore When you see the abomination of desolation spoken of by Daniel the prophet standing in the holy place Whoever reads let them understand Then those who are in Judea flee to the mountains Let him who is on the housetop not go down to take anything out of his house and Let him who is in the field not go back to get his clothes As we look at Matthew 24, let me remind you and again I'm going to lay some foundation for us so that we can move into a better understanding of what Jesus is speaking of here in Matthew 24 We know that in Matthew 24 Jesus is answering a question that has been posed by Peter James John and Andrew The question that they had asked is found in verse 3 of chapter 24 when they said Tell us when will these things be and what will be the sign of your coming and of the end of the H So Jesus is answering this question and he begins to outline conditions That will exist prior to his return He started with events that begin in what is called the church age and he said these are signs There'll be an increasingly widespread spiritual deception. There will be wars on an international scale there will be famines there will be pestilence and Earthquakes and this will all be on the increase in verse 8 Jesus said These are the beginning of sorrows. In other words, these things are the initial indicators that there is more to come soon Now Jesus initially outlined general conditions that would exist When we got to verse 9 the word tribulation was introduced He said then they will deliver you up to tribulation and kill you and you will be hated by all nations for my name sake and so the word tribulation needs to be considered for a moment because on the one hand there is a Tribulation that every believer encounters when you look at the word tribulation in the original language because we need to remember that The original New Testament a language was Koine Greek common Greek When you look at the word tribulation in the original language It literally speaks of affliction. It speaks of anguish distress trouble and Persecution that's how the word is generally used and so on the one hand believers experience affliction as part of our normal Christian life You see to believers Jesus was stating that they would be delivered up to tribulation and even be killed But this tribulation speaks of the kind of tribulation that Believers do encounter you see suffering for righteousness sake is part of the cost of following Jesus Christ and John 16 Jesus said at verse 33 He said these things I have spoken to you that in me you may have peace in the world You will have tribulation, but be of good chair. I have overcome the world So under general life conditions Afflictions are part of what believers will endure We do endure tribulation and as we do so God works in us and he teaches us through it Romans 5 verse 3 says not only that but we also glory and tribulations Knowing that tribulation produces perseverance and so we actually have our faith refined and strengthened and It demonstrates the reality of it as we persevere through these various afflictions we go through that's part of their normal Christian life In second Corinthians chapter 1 verse 4 Paul said God comforts us in all our tribulation That we may be able to comfort those who are in any trouble with the comfort with which we ourselves are comforted by God And so as you go through the afflictions of following Christ and there are many that you will endure You have your faith purged You are strengthened and then you're able to encourage other people who go through the same Somebody once said God whispers to us in our pleasures Speaks in our consciences But shouts in our pains It is his megaphone to rouse a deaf world So believers in the days preceding the return of Jesus will endure tribulation Now during the time specifically referred to as the tribulation it becomes intense There's anything there's something that'll occur I'll point it out again in just a moment, but it's called the rapture and After the rapture there'll be intense persecution against believers and during this time believers converted During the tribulation will increasingly be persecuted There will be false believers who will be exposed and will inform on genuine Christians Deception will be increasing lawlessness will abound But in spite of all of this the gospel will continue to be faithfully preached through genuinely converted believers as well as other means that the Lord uses After the rapture there will be a seven-year period called the tribulation So this time spoken of as the tribulation is also referred to as the time of Jacob's trouble as well as Daniel's 70th week and it can be broken into two sections Tribulation and great tribulation. You'll see that in just a moment. And so what is this tribulation that is spoken of? well, let me give to you some very Basic things some foundational information in order for us to understand what Jesus is speaking about when we get to verse 15 Here's some foundational information five things about the tribulation one the tribulation in scripture is The final judgment of God on a Christ rejecting world It's the final judgment of God on a Christ rejecting world You need to remember that the church is not judged along with a Christ rejecting world because we didn't reject him In Romans chapter 5 verse 9 Paul said it like this He said much more than having now been justified by his blood. We shall be saved from wrath through him You see in in Revelation chapter 6 there are those who are crying out saying save us from the wrath of the lamb The tribulation is God's pouring out of his wrath on a Christ rejecting world, but the church will not be part of it It is also secondly a relatively brief period of time. It lasts seven years You see that in Daniel chapter 9 verse 27 as well as Revelation 11 Revelation 12 as well as Revelation 13. It's relatively brief third It is a period of unrestrained spiritual delusion and human wickedness if we think it's bad now It's going to get worse later It says in verse 12 here in chapter 24 because lawlessness will abound the love of many will wax cold and so it'll be an unrestrained time of wickedness a Fourth thing is that it is a time of Israel's greatest suffering You see that in verses 21 and 22 of this chapter Then there will be great tribulation such as has not been since the beginning of the world until this time No, nor shall ever be and unless those days were shortened no flesh would be saved But for the elect's sake those days will be short It'll be a time of great suffering and finally it occurs between the rapture and the second coming of Jesus Christ now Last week I mentioned the rapture This is an event again that will occur prior to the tribulation in 1st Thessalonians 4 16 and 17 It says the Lord himself shall descend from heaven with a shout with the voice of an archangel With the trumpet of God the dead in Christ shall rise first Then we who are alive and remain shall be caught up together with them in the clouds to meet the Lord in the air Thus we shall always be with the Lord There are those who will say that there's no such thing as a rapture They'll say you Christians use the term rapture and you can't even find it in the Bible see when you look at 1st Thessalonians 4 It speaks concerning being caught up. It doesn't say raptured and thus they'll say it doesn't say rapture It says caught up and thus you've made up or invented Something that isn't even found in Scripture when we need to know that the New Testament used the word harpatsu The word harpatsu in the Greek speaks of seizing or taking something forcefully away When the New Testament was translated into Latin The Latin word was used to describe the Greek word harpatsu and the Latin word is where we get the word rapture from And so the Bible speaks concerning an event called the rapture. There is nothing Prophetically that needs to be fulfilled until that event takes place. I was with Pastor Chuck Smith Before he went to heaven and he and I were on up on the to every man and answer program that is broadcast on K wave and Pastor Chuck was normally on that answering biblical questions and on Occasion you would ask others to come and join him and on this one particular time I went with him and and joined him and I Had a great time one of the questions that was asked Came in from a caller from Chino. I still remember that I was seated across from Pastor Chuck and and they said we have a caller from Chino and this was years ago now and and so the voice comes over the phone and says hi pastor Chuck and I wanted to ask you a question and as I was seated there. I thought I recognized that voice I'd like to ask you about tattoos pastor Chuck is it a sin to get a tattoo and Chuck answers and says no, it's not he says. I don't know why you would but no it's not a sin He said thank you pastor and I said wait a minute David. It was my son. I Said I Said I said it may not say you can't get a tattoo, but it does say honor thy father and thy mother, okay? But we were answering questions together and one of the questions that was asked was What needs to be? Accomplished in terms of just the prophetic overview What is the next prophecy that that will be fulfilled in and Chuck? Immediately pointed out that the next prophecy in the Bible that needs to be fulfilled will be the rapture The rapture is there's nothing that is to be fulfilled prior to that That's the reason why we use the word eminence We believe that that is something that is imminent. It's about to happen. It's just even at the door The next thing that happens is the rapture of the church We are not entering into the pouring out of the wrath on a Christ rejecting world because we did not reject Jesus Christ When Jesus was speaking in the book of Revelation in chapter 3 He gave a promise to the church of Philadelphia He said in Revelation 3 since you have kept my command to endure patiently I will also keep you from the hour of trial that is going to come upon the whole world to test those who live on the earth The church will be kept from the trial that comes on the whole world We're gonna be taken when Jesus removes the church and then he begins to pour out his judgment on those who have rejected him So when we get to verse 15 here in chapter 24 He says therefore When you see the abomination of desolation spoken by Daniel the prophet Standing in the holy place now notice whoever reads let him understand Then let those who are in Judea flee to the mountains Let him who is on the housetop not go down to take anything out of his house and let him who is in the field not go back to get his clothes and So as the Lord is speaking here He's pointing out that the church will be kept from the hour of trial But he's giving now a key sign that's related to his second coming notice He said in verse 15 again when you see the abomination of desolation He's not speaking to these men by the way He's speaking to future believers because notice how it says in verse 15 whoever reads let him understand This is to future believers Remember that he had been questioned already concerning when the temple and all would be destroyed Because the temple was destroyed and yet he's speaking as if the temple is in existence Because it will be rebuilt in the yet future and that's why those of us who are reading need to understand these things and So he's speaking here concerning the abomination of desolation notice prophesied by Daniel standing in the holy place Let me develop this with you a little bit further prior to the rapture Prior to the rapture comes a progressive promotion of deception this deception will permeate the world and This deception promotes a rejection of the gospel during the church age Believers are to continue to live the gospel and evangelize but over time the church will be infiltrated with false Believers Jesus and Matthew 13 referred to them as as tears So the purity of the church begins to be compromised with sin becoming Acceptable and that's already taking place in our day. By the way sin has become acceptable. I was with several pastors recently back east and We were conversing concerning the condition of the church One of them was mentioning to me And I won't give any names because I don't think it's proper to do that at this point But it was mentioning to me concerning some well-known television personalities and how It was a there was a there was a cruise that was set up for Christian TV personalities and worship leaders. This is just this happened recently and They were sharing with me about the condition of the church and they were saying that there was one particular Person who went on that cruise who's a worship leader well known and While he was there several of and if I gave you the names of these people you'd know They had an open bar and these TV personalities younger guys were busy drinking and one of them got so drunk He turned to this other fella and said to him Man, I'm gonna have a hangover tomorrow How about you and this other young man said no, I won't have any hangover. I don't drink and It was in the context of conversation of how certain things have infiltrated the church and become acceptable to the degree That even those who are well known for promoting on TV messages Are very often not living out those messages and they're living in a carnal way And what we have today and this can kind of sounds I know it's gonna sound Hateful and this and that and that's okay I'm used to that. I'm a very hateful guy But that's a bottom-line kind of thing is that The church because it isn't being taught Because the church isn't being taught The word and because people no longer endure healthy teaching they don't want to put up with it They want to hear things that tickle their ears because that is true and Paul said it I'll show you that in just a moment. What happens is we begin to judge the reality of whether or not God is present Not based on whether the people actually are being formed into the image of Christ Not not based on whether the people who attend that church actually are sincere in their faith and are and are Maturing in the things of God not based on the things that you see that are actually what we call the marks of the church In the book of Acts chapter 2 verses 42 through 47 where they were Constantly steadfast in the Apostles doctrine breaking a bread in prayers where God was moving they were in fellowship It was just a wonderful wonderful thing the church in the early date was was was being used by God in mighty ways And and the gospel was flowing from Judea Samaria And and into the uttermost parts of the earth well the church is in the last day is getting caught up with the Infiltration and what happens is through the delusion of false teachers It ceases living in a holy fashion and because it is ceasing to live in a holy fashion It's actually not giving the message that will save people and so what he's speaking about is that there'll be a Deception that takes place and it promotes a rejection of the gospel and that believers will be Are supposed to continue to live in the gospel and evangelize but the purity of the church begins to be compromised with sin Because it becomes Acceptable this is all coming through according to verse 11 false teachers false teachers who continue to arise and false teachers who continue leading people astray and as mentioned first Timothy 4 verse 1 the spirit clearly says that in later Times some will abandon the faith and follow deceiving spirits and things taught by demons This promotion of deception is fueled by the influence or the spirit of the Antichrist in first John 4 3 it says every spirit that does not acknowledge Jesus is not from God This is the spirit of the Antichrist which you have heard is coming and even now is already in the world this influence encourages the rejection of Jesus and results in the accepting of Antichrist and This rejection is propagated by false prophets and it leads to the worldwide acceptance of this figure that is referred to as the Antichrist so after the rapture false prophets continue to abound they continue promoting Antichrist at that time The man of sin will be revealed. He is called the son of perdition When you read your Bible you see the Antichrist We know him best by that term, but he's also referred to as man of sin also called son of perdition He is the lawless one He's referred to as the beast the little horn the wicked one and also the willful king and this one's going to be accepted Because the world will be prepared for him by false prophets when you look at your Bible You discover that he begins in a non-threatening way. He develops a following and It is at that time that he signs a covenant with Israel the first few years the first three and a half years or so of his quote-unquote Rule is he'll be looked at as being a man of peace He even is going to broker some kind of covenant with the nation of Israel It says in Daniel 9 27 he shall confirm a covenant with many for one week But in the middle of the week he shall bring it in to sacrifice an offering So that tells us that there will be a covenant that is signed that allows sacrifice and offering to take place and yet That temple is not rebuilt. It's not built yet So that tells us it's the last the day last days that he's speaking about and he says in the wing And on the wing of abomination shall be one who makes desolate even until the consummation Which is determined is poured out on the desolate. That's what Jesus is speaking about in verse 15 when he says the abomination of desolation I've mentioned to you that the covenant covenant most likely will include the rebuilding of the Jewish temple But in the middle of the week in the middle of the tribulation which is broken into tribulation and great tribulation in the middle of The week he breaks the covenant. He's going to demand worship in the temple He's going to declare himself to be God and second Thessalonians 2 verse 4 it says he will oppose and will exalt himself Over everything that is called God or his worship so that he sets himself up in God's temple proclaiming himself to be God To perpetuate that He has an image that is made and his images commanded to be worship in Revelation 13 verses 14 and 15 it says the false prophet deceives those who dwell on the earth by these signs Which he was granted to do in the sight of the beast Telling those who dwell on the earth to make an image to the beast who was wounded by the sword and lived He was granted power to give breath to the image of the beast that the image of the be should both speak and cause as many as Would not worship the image of the beast to be killed This makes up the abomination of desolation spoken by the prophet Daniel Is it possible for something like that to happen today? Absolutely. Was it possible during the day of the writing of the gospel that there could be an animated statue of some sort that speaks and People would actually do homage to No, this is something that happens in the last days and that's why we would get this Addendum whoever reads let them understand Somebody said Jesus was not giving warnings to the disciples themselves or to their generation, but to believers in the end time who would read this and Would need to be strengthened That when this happens by the way, Israel is going to be taken by surprise and intense persecution Will begin in 1st Thessalonians 5 3 while people are saying peace and safety Destruction will come on them suddenly as labor pains on a pregnant woman and they will not escape Antichrist declares himself God that precipitates the three and a half years of great tribulation This occurs in his last three and a half years. What are you to do? Well verse 16 Let those who are in Judea flee to the mountains Let him who's on the housetop not go down to take anything out of the house Let him who is in the field not go back to get his clothes. What are they supposed to do? They're supposed to not be caught up with material things They are in immediate danger Antichrist is set up operational headquarters in Jerusalem So those in Judea are to flee you're to run for safety you're to take flight In order to escape the danger not every Jew will be successful in escaping But some will and they will be converted in Zechariah 13 8 and 9 It says in the whole land declares the Lord two-thirds will be struck down in parish Yet one-third will be left in it this third I will bring into the fire I will refine them like silver and test them like gold They will call on my name and I will answer them I will say they are my people they will say the Lord is our God We have seen Holocaust in in the history of the United States This will be intense persecution to the destruction of so many those who survive and trust in him Will be his covenant people Jeremiah 31 33 and 34 says this this shall be the covenant that I will make with the House of Israel after those days says the Lord I will put my law and their inward parts righted in their hearts And will be their God they shall be my people they shall teach no more every man his neighbor And every man his brother saying know the Lord for they shall all know me from the least of them And to the greatest of them says the Lord for I will forgive their iniquity and I will remember their sin No more So God is going to provide a place for them to flee to notice with me in verse 16 It said let let then let those who are in Judea flee to the mountains When you look at revelation chapter 12, especially right around verse 14 It speaks of God preparing a place for them To be safe When you combine that with Isaiah 16 1 through 4 it appears that God is going to open up a place in Jordan And the place that he will open up is going to be in a city called Petra And there will be those who flee into Jordan And are protected in Petra In Isaiah 16 it says verses 1 through 4 send the lamb to the ruler of the land from Petra to the wilderness to the mount of the daughter of Zion for it shall be a wandering bird thrown out of the nest So shall be the daughters of Moab which is Jordan at the fords of the Arnon Take counsel execute judgment make your shadow like the night in the middle of the day Hide the outcast do not betray him who escapes let my outcast dwell with you. Oh Moab Oh Jordan be a shelter to them from the face of the spoiler for the extortioner is at an end devastation ceases The oppressors are consumed out of the land so he says flee and they will flee from Judea and many of them more than likely will cross And go into Jordan notice how it says in verses 17 and 18 Let him who's on the house top not come down to take anything And not to return from the fields to pick up anything.  What is it that you have what will a man give an exchange for a soul? Jesus said And he's saying i'm warning you in advance these things are going to take place The persecution is going to be intense. There will be people who are slaughtered You're going to be fleeing you need to get out. You need to get away Don't even come down from your patio. That's over your roof where you where you sit during the summer and it's cool Much cooler than being in the house get out if you're in a field and you hear these things are taking place Don't return to pick up something just leave. What do you have that matters to you more than your life? And that's the whole thing. He's basically saying don't cling to the things that can't save you This is another thing that we by way of application today should should remember And and and yet we we don't sometimes we don't remember that that the things we have Though they're they're nice to have but they also perish with the using and we fail to remember that Sometimes we really do think that if we get that cabin or if we get that car or if we get that pool If we get that whatever it's going to make us happy and yes, of course There's certain satisfaction and there's nothing wrong with having that cabin There's nothing wrong with having the nice car or the pool of course not But when that becomes my life goal and I think that by having these things i'm going to be satisfied Then it just takes a little while for you to be able to obtain a goal and to realize That it really it doesn't satisfy all it does is what your appetite for something else.  It's got to be this model. It's got to have these things You finally save for a few years you finally get the model and then the new model comes out the next model year And you go, oh man, if I'd have waited one year I'd be able to have instead of 400 horsepower. I'd have 450 horsepower. Oh, and it's and that's what we do That's what we do and I've said this more than once, you know the junkyards And trash places are are filled with our treasures the things that we really needed to have And once we got them we had them for a while. We put them in the trash and now there's somebody else's treasure That's what we do and that's so basic. That's so commonsensical and yet the church Has to be reminded of that Somebody said the possessive clinging to things must be torn from our souls in violence Even like when jesus expelled the money changers from the temple has to be expelled from our souls Because it is so entrenched So God is heard Of the evil that has taken place in Sodom and Gomorrah and the surrounding cities and he's come to see What has taken place and there's a man Who has come to sojourn in Sodom Who has actually become a person who sits at the gate He has a family His soul Peter tells us was a righteous soul That was vexed constantly by the sinfulness of the city that he lived in Angels come and speak to him and say You need to get out and you need to get out now Because god's bringing judgment He's got a family wife children some daughters who are married He begins to speak to them say we got to get out of here Because the evil is coming and god's judgment is going to deal With this We need to go And two of his daughters who are married say No, there's no way we're going to stick behind but he's got two unmarried daughters and he's got a wife She's not even mentioned. She's just misses lot And she leaves with him But the bible very distinctly says that as they had left the precincts they had been told Not to look back But to get out Because judgment it was going to fall and the bible speaks how lots wife Turned to look and was caught in the judgment When I first read that as a young believer, I thought just turning in looking But when you begin to study the passage and you look into the commentators in the original language You discover something it wasn't that she glanced over her shoulder just to make sure nobody's following Is that she planted herself in such a way as to long to return to the place she had just been delivered from In other words, her body wasn't in the city, but her heart remained there And because her heart remained in that place she was caught in the judgment of that place Just because somebody comes to a church doesn't mean their heart isn't still in Sodom That's the point and that's why Jesus said in Luke 17 32 remember lots wife Remember her Remember lots wife, and then he said whoever tries to keep his life will lose it whoever loses his life will preserve it Remember lots wife become detached from this age Don't leave your roof to go and get something don't leave your field to come and retrieve something when you hear these things that take place Fully because it's coming and that's what the Lord is saying here Notice how he says in verse 19. What are those who are pregnant and those who are nursing babies in those days? It's going to be difficult for them. That's why he says woe unto them It's going to be difficult. You mamas and pregnant women will not be able to move quickly Pray that it's not on the Sabbath he goes on Why or winter? Why because winter brings severe conditions and and on the Sabbath that tells us that the Sabbath is Enacted because legalistic Jews will impede their flight And then he says in verse 21 In verse 21, then there will be great tribulation such as not been since the beginning of the world until this time No, nor ever shall be unless those days were shortened. No flesh would be saved But for the elect's sake those days will be shortened There will be great tribulation in daniel 12 verse 1 there will be a time of distress such as not As as has not happened from the beginning of nations until now great tribulation Great tribulation the escalating judgments on man The the judgments demonstrating the wrath of god They're enumerated for you if you'd like to read about it on your own in revelation chapter 6 through 19 Yet he says the elect's sake This speaks of redeemed Israel as well as Gentile converts unless those days were shortened The earth would be annihilated Now he goes and finally Verse 23 if anyone says to you look here is the christ are there do not believe it For false christ and false prophets will rise and show great signs and wonders to deceive if possible Even the alexi i have told you beforehand Therefore if they say to you look he's in the desert do not go out Look he's in the inner room do not believe it For as the lightning comes from the east and flashes to the west So also will the coming of the son of man be for wherever the carcass is there the eagles will be gathered Together If someone says verse 23 look here's the christ people have fled to the mountains They're going to hear rumors that jesus returned false prophets Will be performing miracles In an attempt to draw people out Again, there are many today Who look to miracles as evidence that god exists and indeed god performs miracles. There's no doubt about that But the world is already being set up to receive the false prophets And the antichrist because the miracle is looking for some kind of proof that there is a god And in many people's minds The supernatural is always an evidence of the reality of god And sometimes you will have people who believe in things that are not in the bible But they say well, I have to believe it because I've seen it or I've experienced it myself When in fact because they're not taking scripture and and using scripture as As the proof text for whether or not you can believe those things. They just believe based on their emotion It's interesting how that when the day of pentecost had fully arrived You see it in the book of acts On the day of pentecost that had fully arrived and the people had been baptized in the holy spirit And the hundred and twenty who were there in an upper room according to acts chapter two Spelled out of that upper room and they were speaking in in supernatural languages languages that had been given to them by By the gifting of the spirit himself. They were unlearned languages but They were speaking in the tongues of so many people who were there And asked they even so far as to ask the question how how how can they speak this way having never learned our language And when this is all happening, there's a mocking that takes place. Oh, they're just filled with new wine In other words, they're drunk when the apostle peter stands up to speak and that great pentecost sermon He begins by saying these men are not drunk as you suppose It's too early in the morning the bars aren't even open And then he does this he gives a scriptural Explanation this is that which was spoken of by the prophet joe who said Any supernatural manifestation must have a scriptural explanation And unfortunately because people today don't know scripture They fall for the deception And they're going to be saying oh christ is here, but jesus is saying no you're in hiding They're going to try and lure you out Because you desire to be released from all that's going on and to see me Do not do it You see under the pressure of the time they want to be with him False signs and wonders will occur in order to catch genuine believers It's satan's last effort to destroy them In second chrithians 11 13 Paul said such men are false apostles deceitful workmen Masquerading as apostles of price and no wonder for satan himself masquerades as an angel of light It is not surprising then if his servants masquerade as servants of righteousness Their end will be what their actions deserve in verse 26. He simply says do not believe it Why well verse 27 He says for as the lightning comes from the east flashes to the west So also will the coming of the son of man be it's going to be sudden And it's going to be obvious It is going to be sudden and it is going to be visible It isn't going to come through people saying oh christ is here. It's going to be something everybody sees In revelation chapter 1 verse 7 it says this look he's coming with the clouds Every eye will see him Even those who pierced him all the peoples of the earth will mourn because of him. So shall it be amen Every eye will see him We will see him and he's saying when he comes it's going to be obvious It's not going to be that he's in a desert. It's not going to be that he's in the inner room It's going to be something you'll see it. It's sudden and it's obvious Keep that in mind because I've mentioned this to you before but it bears repetition The Jehovah's Witness an organization that goes door to door and talks about the last days and this and that Well, Jehovah's Witnesses are taught that in 1914 Jesus received his crown and began to reign invisibly One of their periodical says this I'm quoting their periodical although it occurred invisibly to our human eyes in the heavens Yet it was in the year 1914 That they were given to the son of man all that rulership dignity and kingdom They believe that Jesus received his crown and began to reign invisibly in 1914 Jesus said no Jesus said it's going to be sudden and it's going to be obvious and all people will see I'm not doing this invisibly I'm not doing this in hiding. It will be done openly And he finally says in verse 28 wherever the carcass is there the eagles will be gathered together Remember that an eagle is really a vulture It's carrion. They feast on the dead He's saying that the world will be reduced to a lifeless corpse lying unburied Surrounded by the end of the great tribulation the world will have been terribly judged You'll be like a lifeless carcass in a wilderness And ultimately Jesus will be its judge That's why Hebrews 10 31 speaks in this way. It is a fearful thing to fall into the hands of the living God He has said to us I tell you these things in advance Let not your heart be troubled. Neither let it be afraid Do you believe in God? believe also in me My father's house or many mansions if it were not so I would have told you I go and prepare a place for you and if I go and prepare a place for you I'll come again into you and receive you unto myself That where I am There you may be also The next prophecy to be fulfilled is Jesus taking the church to be with him These things are not things that you have to go through I've been asked do you think that this is soon? And I have to say what Jesus said is coming is even at the door Is it soon? Yes. Well, didn't you believe that when you first got saved back in 1970? Yes Well, it's been a long time Yeah, that simply means is coming as sooner Just means it's even closer Are you ready is the question? Are you ready? Listen, you may look at this as being just kind of just something in some old book It's absolutely true We are seeing Days that are evil We are seeing things today aren't we that We're not even mentioned in polite society 50 years ago 60 years ago There are things on tv. You just regularly tv that you turn on And you see today unfiltered uncensored That you would you would never have seen even in your parents generation in my generation I mean we come from a time some of us come from a time when when not that many people even had tvs I come from a time when we actually went to my aunt's house to watch color tv We didn't have color tv and she had a huge tv. It was 19 inches Amazing And we saw the beetles on it We come from a time when lucille ball and desi arnez on the i love lucy show They didn't even sleep in the same bed and yet somehow they had little ricky. We never figured that went out It was just that way, wasn't it? I mean that's the way it was You didn't have toilets flush until archie bunker flushed the toilet In all in the family and that was looked at as revolutionary tv So the things that some of you who are younger have grown up with Has calloused your soul You're callous to things you're used to seeing things like janice jackson Popping out of her top on the super bowl and things of that nature Where people they used to go and they would they actually police actually arrested Jim Morrison from the doors for lewd behavior on a stage You used to go to college to learn Things that would help you in life. We live in a different time You didn't parade For perversions You didn't give people permission to believe that if you want to be a male even though you're a female That's what you feel you are We have come into crazy days crazy days That are looked at as being normal and when people like me stand up and say you realize of course that we should pity those who are So deceived my heart goes out to them because they're so messed up But that view has always been recognized as kind of kind of crazy way to think It's an improper way to think because it's not real I mean I could stand up here right now and tell you that i'm a six foot eight black NBA player and if I want to believe that who are you to tell me i'm wrong That's what I believe It's you're you're gonna believe your eyes or you're gonna believe me And that's that's what we're living in right am I wrong am I wrong? It's crazy But we have come we have come to a place where we accept anything Anything that comes down the pipe we believe it I don't Because I have a book that is inspired by god who teaches me truth And helps to separate the darkness from the light We have not been deceived We believe god's word god never lies he tells the truth because Because of that when we speak the truth we are haters Remember with me that in the early days of the church We were called haters of mankind And the reason we were referred to as haters of mankind it was a charge against the church Part of the reason is because we actually spoke what the bible said concerning life And oh we were so opposed to what was being said by the common intelligentsia of the day Well, guess what that's happening to this day.  You really believe that? And the answer to that is Well, yes, I do Yes, I do Listen, if you don't believe in god who can preserve his word My god doesn't lie and my god is able to preserve his word It's the most important thing in the universe the word of god It's a message whereby a man must cling to in order to be saved Are you saying that if there is a god? He's not capable of giving us his word He is capable of giving us his word not only that he is capable of transforming lives by his word and by his power And that's why we're prepared and that's why we will not accept the antichrist We will receive jesus christ because listen my children and my grandchildren now my grandchildren They will receive either jesus christ or antichrist I'm raising them to receive jesus christ the true christ who will set them free that comes from this book. That's how it works


Hold on. Stop scrolling. If you care about the future of our world, give us a minute of your time. We would like to think that if future would include happy and healthy children who live in a world that's easy to make a healthy choice. Unfortunately, right now, one in three Caribbean children is overweight or obese. And without effective policy, this is projected to reach 50% by 2030. If you're still listening, that means that something we said is still going to keep listening. As young people passionate about health, we want to bring awareness to what can be done to protect the future. Us. Specifically, policies that can help create a healthy school environment. A school environment that is free of sweet drinks and the influence of the ultra-processed food industry. We need protection from the pervasive and predatory marketing strategies of companies that use us children and young people for their unhealthy products. Would you want these type of foods to be marketed in schools or made easily accessible to us as children and young people? So, really, what are we asking for? Really, what are we asking for? So really, what are we asking for? A healthy school environment. A healthy school environment. A healthy school environment. A healthy school environment. We're calling on all youth to take charge of stakeholders in their health and to use their voices and platforms to amplify these messages. We are all calling on governments and NGOs to ensure that we, young people, are engaged meaningfully at all stages of any action on the future of our health. We have power. We have power. We have power. We can make a change. We can make a change. We declined for a healthy and safe future. That's Unite for a healthy and safe future. That's Unite for a happy and safe future. Do this for...