Welcome everybody to the 42 Courses podcast. I'm really delighted today to be talking to Alice Sherwood. Alice Sherwood is the author of Authenticity but has many other strings to her bow of a very, very interesting career in many areas the arts, business, TV documentary, most lately, trustee at Hay Festival. And of course, now, do you give yourself the title? Is your predominant title author, Alice, when you introduce yourself? Well, thank you. Thank you for that. And it's brilliant to be here. I would say two things. One, I'm attached to the Policy Institute at King's College London. So I have the catchy title of visiting senior research fellow at the Policy Institute at King's, which is quite difficult to say with a single breath. And, but I would say author as that being the most recent and relevant, I think. And Alice, when we first met, which was back summer of 2022, it was just as the book Authenticity was being published. And since that time, you've gone on a long journey as it were with the book and traveled the length and breadth of Britain and visited Ireland, I know, talking at festivals. Maybe you can just kick off by telling us initially what you felt your aim was with the book and then maybe we'll move into where possibly your line of thought might have developed and changed over these last couple of years. Well, there were two real reasons for writing the book, the germ of the idea was something very personal, which was that many years ago, I found out that one of my best friends, who was also my boss, was a complete fantasist and a fabulous and everything he told me about his life from that he was related to aristocracy, that he had a terrible tragic illness, that he'd been a member of the security services, all of these rather dramatic life stories, none of them were true. So that really set me off, but there were a great many other things once you start getting interested in what's real and what's not real from art to what does it mean to say work of art is authentic to brands, big brands very much selling themselves on authenticity and obviously technology and the changes it's done now it's caused with the authenticity of information. And I think the umbrella term if you like there is that we all say what really fascinates me is we all say how important authenticity and the pursuit of authenticity is to us. You know, it's almost a spiritual quest, we want to be authentic, we want to live our best life, we want to live our real life and yet we've created this world that is arguably less authentic than ever before. And so when I tell the stories in the book because it's made up of stories that was really what was on my mind, which is can we understand the big forces? Why are we doing this? You know, why do we say one thing and do another? And of course the essence as you say of what started off your exploration into authenticity is of a shocking story, Alice. You know, for people unfamiliar with the story, you know, it's the equivalent of the type of story that one would only expect usually to come across in like, you know, a Netflix series. It's quite a shocking experience that you went through, Alice. Well, they should make a Netflix series of him. I've called him Alistair, obviously that's not his name, but everything else is true because he was this fantasist who made up stories and he more or less deceived everybody. And importantly for me, he deceived two of my friends that he got engaged to simultaneously, which put me in an awkward position and them in an awkward position because they didn't know about each other. And over time, because when Bush came to Shav about having two fiancés and you can't really have two fiancés at once because sooner or later you're gonna have to, there'll be a date in this case, New Year's Eve 1999 when you will have to either be with one or the other and the other will be quite cross and start wondering why. But fast forward about 20 years during which I didn't see him because he vanished after the fiancés episodes. And you say something you might see on Netflix or read about in a paper, I literally opened the paper and it said, company director stole millions. So he turned up again. And I think that's one of the interesting things about the essence of someone who is a con man is they don't just con or lie once, they just do it again and again and again. And that is, well, for me, that was a very important point to understand. And of course, as you said, the book is very much made up of stories delving into the meaning of authenticity in many different areas. You dip into business, you dip into advertising. What I'm curious about at this stage, Alice, as I said, you've spent two years with this book now talking presumably to thousands of people. How do you feel, where are you at now in terms of your feeling about authenticity? Has your, have any opinions changed? Have any dynamic news stories emerged? Have my feelings changed? No, except so many people come up to me after and tell me about the imposter they knew or the con man that they knew. So it is much more prevalent than you might have thought. One of the things that has changed, what was interesting was which areas I was asked to talk about. Definitely imposters and con man. Everyone loves the con man, especially financial audiences, by the way. All the big finances, how will you please come talk about, you know, how to be a con man or rather, sorry, the anatomy of a con. And people are interested in authenticity and art and brands. Nobody has asked me to talk about but I think the Guardian have put somebody, not Guardian Prospect have put a very good journalist on the story about fake drugs, falsified drugs. And of course everybody wants to talk about tech and I wrote about mainly about the internet deception and I wrote a little bit about AI because at that time it was only chat GPT2, not free and you could only get hold of it if you were a researcher. So I played around with it and I was very impressed but I didn't write about AI. Now, all anybody wants to talk about is AI. And that is really interesting because it has thrown up so many issues.  And at that point, all your issues about identity. Identity is really, as it were, an up and coming subject because however difficult the internet made it with identity theft, AI just turbocharges it. So that would be the big change. Of course. And that was such a major, a major development, chat GPT being released for public use and the speed of creation of the new apps and ways in which it can be used, which as you say, was just very much in its fledgling state when the book was published. But also the other thing, obviously, the big C that we can't not mention, it was published very shortly after COVID. And I think to what degree do you think that that had an impact on our wanting to be authentic or do I mean showing our more authentic selves by sitting as we are now in our front rooms at home and chatting rather than in a sort of swanky studio or in a boardroom? Are we more ourselves? I think that's really interesting. I mean, when I wrote it during lockdown, wrote up my research as it were, during lockdown, wrote the stories. And I thought that COVID would be the end of internet misinformation, at least I did at first, because I thought you can't actually lie about a matter of life and death. So I was incredibly wrong. One thing it did do was give extra oomph, very big extra oomph to all the efforts and the alliances on the web who might have individually been fighting misinformation. They all joined up together. So actually it made the fight against information much more misinformation, much more powerful. And then yes, it did that strange thing that we all got to see each other much more without the kind of disguises and the face we, the work face we put on, which I think is really interesting. And I think the effects I've seen of that are twofold. There was a small and particular small, no, but it was American, particularly, I know you have many listeners in America, that the Authenticity at Work movement was primarily American, having come out of Bill George and True North in Harvard. But after seeing people as their home selves, I'm assuming a home self is more authentic self, in work conversations, I think it got extra velocity over here because people were stripped of their pretenses and stripped of their, you can't really wear a tight jacket and you can pretend, in fact, you've shown me how to put false backgrounds you know, onto your Zoom, but that would seem to be very bogus. So I think people became more relaxed and if that relaxed means authentic, I think that's very interesting. And people lobbied more to bring the right to bring themselves, their characteristics and their problems and their needs to work. And the last thing I think that is really interesting and I'm not a great, you can tell by looking at me, I'm not a great fashionista, but I do look at the fashion pages and the constant refrain is, since the pandemic, work is much more dressed down, it's much more casual, it's much more you, it's much more individualistic than it would have been. And I think that is a change. That's so interesting, Alice. And also it's making me think, I mean, we speak with so many people in advertising and in marketing and in PR and in, to a large extent, you can sort of be within your own vacuum, but I don't think anybody would say they've missed, for example, the Dove campaign that shows real women. And I know you do talk a bit about authenticity within advertising and within marketing in the book. And I wondered sort of somebody on the outside of that industry as it were, to what degree you think, or you get any impression that the industry is trying to be more authentic in its work or not. I think what the industry has done is that it's moved on, as it were, from where it was in the second half of the 20th century, where the real innovation there was to sell brands as having personality, which was a very new thing to add personality to a product. So I write about, I think it, gosh, I'm trying to remember, I think it was Omo, the clothes washing powder, which was marketed as your wash day friend, which is quite odd if you actually step back and think about it that some powder will be your friend, but we know what they mean. And I think obviously the big change in our time has been purpose and adding in making your brands have a purpose both for themselves and presumably in the hope that it will resonate with your customers, so that you have Harry's razors who give 1%, I think of their, I don't know whether it's their income or revenue, to men's mental health charities, and you have a lot of sustainable brands, and then you have some people slightly pushing back on that. I think it was when Hellman's, is Hellman's Unilever? I think so. Anyway, when Hellman's decided that they were going to add purpose to their brand, and there were quite a lot of emails saying, come on, the purpose of Mayo is just to go on your sandwich, please, you know, don't push it, but actually they did have some point, which is actually if you put anything, any leftovers in your fridge with Mayo, mix up with Mayo on bread, you know, you've stopped wasting food, you've eaten it instead. So they had a good point. So I think purpose, adding purpose into your brand, which feels more authentic, I think, I'm not sure whether it always is, and that thing of encouraging you to choose brands as though they were your friends rather than products. My, you know, Harry's razors, well, my mates would give to charity, so I'll use Harry's razor. Well, that makes sense, and it doesn't make sense. So I think that's where I, as an outsider, every time I look at those and I get a warm feeling because, you know, somebody's going to plant a tree if I drink their vodka, and then I think, well, hang on a moment, I could drink their vodka and plant a tree myself. So, you know, the test must be in whether they do actually plant the trees, or whether they do actually give the money, and to see whether it's not just window dressing. This is just a non-advertising person. You have to tell me what advertising people think. Does it work? I presume it does. And last time we spoke, Alice, you weren't long back from actually visiting Dublin, where you were invited to speak at a gallery that was hosting an Andy Warhol exhibition of which there's a whole chapter within your book that a man who will not lay down, we consistently are fascinated with him. Maybe you'd tell us a little bit about that event, Alice? Yes, I will. It was an absolute thrill. It was at the Hulane Gallery, which is the, well, started, it's, why am I telling you what the Hulane Gallery is? You live there. Anyway, it's a very distinguished gallery of 19th, 20th, and 21st century contemporary art, and they'd had an absolute blockbuster, or having an absolute blockbuster of a Warhol exhibition, 250 works, and it was just extraordinary, extraordinary and beautifully laid out, and they had a day of talks. And my one was about how Warhol really upended our idea of what it means to be an authentic painting, what makes an authentic picture. And he did that, and I was first drawn to it by just a quick quote I read somewhere where the author was gushing about Andy Warhol's pictures and how much he loved them. And Andy just said, oh, well, I feel like my pictures, you know, meet Gerard over here because he painted most of them. And I found that very intriguing because in that case, if Gerard painted most of them, in what way are they an authentic Warhol? And then I delved deeper, and it became more and more interesting because Gerard Melanger was Warhol's assistant for years and years and years. When they, at the time, they produced the most famous screen prints, the screen print of Marilyn, the Liz Taylor's, the multiple Elvis's, the car crashes, all the ones that you would recognize. And in the main, Andy would, if you know about silk screening, which is just really, God, any artist out there, you'll kill me, but I'm simplifying, is really stenciling. It's sophisticated forms stenciling.  So you had a mechanically reproduced image of a mechanical photographic image. And quite often, Andy just issued the instructions. So you have a great problem of what makes Warhol, especially when he issued instructions to a printing works that wasn't even in his studio, or in the case of the story, one of my favorite stories, was when his assistant Gerard fell in love and went off to Rome to follow the girl he was in love with, ran out of money and did the whole thing himself. Instead of Andy choosing the photograph, Gerard chose it. He ran off prints, et cetera. And he got a Warhol show at a gallery, which all went very well until the gallery discovered that these weren't exactly Warhols. And at which point he was telegramming Andy going, please, please, please, tell the gallery owners that they're Warhols. And finally, Andy did. What Andy said is, yes, they are Warhols, but you send me the money, not Gerard. So he was pretty canny. But the point being that at that point, something that wasn't a Warhol becomes a Warhol, even though Andy never touched it, because Andy said it was, because Andy telegraphed saying a picture he never made, he never saw was a Warhol. So like an act of God, it becomes a Warhol. Well, that's not how we understand what makes an authentic painting, is it? So I thought it was completely gripping. And then there was another story of, by the time that Andy had really got or begun to get into the habit of just sending instructions to a printing place in a screen printing place in New Jersey, he instructed a series of 10 prints of self-portraits, again, which he didn't make, he didn't touch, he never saw until they arrived back. And 20 years later, just after he died, when these were very, very, very valuable suddenly, then it became incredibly relevant about whether that counted as authentic or not. And at that point, the authentication bureau set up by the Andy Warhol Foundation suddenly decided they weren't. So you have a very fascinating story of this character called Joe Simon Wheelan who had sold his house because he'd been a friend of Andy's and he'd sold his house to buy one of these pictures, decided to sell it when it could be worth two million. And suddenly, even though every friend of Andy's, the foundation, everybody said this was authentic, the official people just denied all over it and made it completely worthless. So I think he's completely fascinating. And for this talk, I also had a look at all the very many ways that Andy stays relevant now. And you talk about Netflix, did you see the Netflix series, there was a Netflix series of his diaries? Only because you recommended it to me in our last conversation, Alice. So I can also recommend it now to anyone who's listening to this. Well, what's fascinating and draws together the various things we've been talking about, is Andy Warhol never wrote his diaries. He, I think, phoned them through or spoke them to Pat Hackett who wrote them down. But what they've done for the series is they've created an AI program of Andy's voice because there's a lot of recordings of him. And they have the AI program of Andy Warhol's voice reading entries from his diary and sounding exactly like him, which is extraordinary that you've got this robot program that sounds exactly like Andy who actually sounded quite robotic. So I thought that was fascinating that he's still relevant. If something's on Netflix, it's relevant. Absolutely. Yes, we seem to certainly have entered into this sort of paradigm of time where it's so important for us to be authentic. Authenticity is given such a weight of value. And yet, as you say, with the birth of chatGBT, chitGPT, that we can so easily use inauthentic tools, which really would just make us more the same as everybody else, the fake videos, the fake pictures. It's really such a paradigm of values that we're all, in a way, having to weigh up to find our own, I suppose, our own opinion of what we think, what's acceptable, is it acceptable to just cut and paste if you've created that text from your original prompts, which I think is a fascinating endless, probably endless, channel we could go down. But what I'm really interested in for you personally, Alice, is the way in which maybe, as I said at the outset, you've lived with these stories for a couple of years now, and obviously there's ones that are sort of, as you said, closer to your heart. But where do you feel we are at today in terms of either the value to us of things being authentic? Where do you think we're at? Where do you see us in mid-2024? Well, my cynical take, in a way, do I mean cynical, is that for most of history, people have believed things that we would now think are absurd, so are absurd and that would never, wouldn't fool us. So we wouldn't say, you know, that we're getting reigned because the reigned gods have reigned on us. So in some senses, we're better off. I think our tendency to believe any old tosh that we want to believe is as strong as ever. So there are, I think there are two conflicting forces. We can, of course, if we put our minds to it and Google intelligently, we can probably find the truth of anything. I was the director of an open-source intelligence company. You can find out anything, it's a lot of work. And you can find out the truth. But our deep instinct to search only for things that we deep down want to believe would probably overpower that. So I think we've got those twin forces. I think it's in a way quite sad that for once in history, we can actually find out whether things are true or not, we're just not doing it. On the subject of the sheer amount of misinformation out there, when I wrote the book, I called the last chapter Armies of Truth and I called the book, How to Reclaim Reality in a Counterfeit Culture. And I definitely saw that we've had time to understand how the internet works and that these armies of truth of all sizes and shapes were beginning to fight misinformation on the internet. And you see whole countries beginning to fight misinformation. Then comes AI. Do we go back to square one? I don't think so, because it took us a very, very long time to react to falsehood on the internet. So I think it was last year that government passed it slightly dodgy, dodgy in the sense of not perfect online arms bills. But I think Facebook started in, was it 2004? But really got going in the mid-2000s. So it took the government 20 years to react. That's just one example to the problems. Compare that to the speed at which we've reacted to the issues of AI. And I think we've learnt something. I think we've learnt, it's not only machines that can do machine learning, we've learnt too that once you see a threat like this, you've just got to move in fast. So I think we're actually in a slightly better place than we were at the turn of the 20th to 21st century. Though facing something that could be horrific, but at least we've learnt that we've got to do something about it. Well, it's a very uplifting note, I think, on which possibly to wrap up this conversation to end it. You always are eminently positive, Alice. And Chris, our CEO, reading your book, said how strongly your positive voice comes through in the book, which I'll hold up here for those when we have it in YouTube. Everybody knows, finally, the book we've been talking about. And Moustache, yeah. Just to wrap up, Alice, as I said, you've spent these two years with the book, your thoughts about things have developed and possibly changed. Where do you think you're going now in terms of are there developments on this theme or new projects? Or are you going completely left of centre in your next direction? It's very, very difficult. I've had one idea which I cannot possibly discuss because I think it's so bonkers that I've actually... My research notes are codenamed bonkers. And I wake up in the middle of the night imagining myself telling my agent that I want to write about this subject. So... Are you an enigmatic, Alice? I have to say, whereas everybody wants to talk about authenticity, I think this would stop the conversation at a dinner. So I have to get it out of my system first. But I think the themes... There will be something similar in the themes which is possibly to do with issues touching on global warming, which is back to the same issue, which is we all know the global warming is happening. We're all afraid of the consequences. Do we act or rather when one actually moves us to act on it? So it's probably something to do with that. I'm sure it'll be fascinating. We'll all be looking on the shelves for a book called Bonkers by Alice Sherwood. But in the meantime, we can all highly recommend that you do read her book, Authenticity.  As we said at the outset, some of them are quite shocking. Many of them humorous, covering many different areas. Know that you will enjoy it and to say thank you, Alice, for joining me today for this chat. It's been lovely to see you again. And thank you for joining us in the 42 course of podcast. Thank you very much indeed. It's been a real, real pleasure.


So, if you want, I can just go into telling you about the products and then we can open there. Yeah, that'd be great. So we had the CES 2021, the online CES. Yes, exactly. So the first thing that I have to show for you today is this PX701-4K projector. This is a home entertainment projector with a full 4K resolution of 3200 ANSI lumens. And one of the really cool features of this projector is that it actually has a mode that allows for a native 240 Hz refresh rate. So that is... Is it connected to something? Can you bring it up to the camera a little bit or...? Sure. Yeah. So it's like for gamers, so what is a 240 Hz? Yes, exactly. So this would be, this would have direct applicability to gamers, specifically PC gamers should be able to connect to the HDMI 2.0 ports on here and get to 240 Hz at 10 MP. Is it one of the first consumer grade 4K projectors with 240 Hz? I don't know if it's the very first one, but certainly it's the first one that we've offered. And we believe that it is the world's fastest projector in terms of response time. So the input lag on this is actually under 5 milliseconds. That's really amazing. You can get the 150-inch gaming room and just game like crazy at 240 Hz, 4K. You need to have a hopefully a fast setup to be able to support that. Yes, you can get very fast. I will say when it is in 240 Hz mode, it will be running at 10 MP instead of 4K. But at 4K mode, you can run it at 60 Hz. 60 Hz. But if you're watching movies, does it go down to 24 or is it just going to do 60 or 120? That's a good question. Mia, do you know if it says it's dedicated to 24 Hz mode for that? Yes, it depends on what the true output can be, 4K, but it really depends on your content. Right? What's the content of source? Anomaly that if your source, your content is 4K and then output is 4K. And does it have HDR and all this stuff? Yeah, this one comes with HDR, yes. Is it a price? I hope it's less than 2400. 2400. I don't know why I say that, but hopefully it's a good price. The price is actually below one grand. So it's $899. So it's a very affordable 4K. One of the most affordable 4K projectors on market and at the lowest input back. Is it true that ViewSonic has had pretty good market share in the 4K projectors? Yes, we do. We do have pretty good share in 4K projectors, especially because we are, what we're trying to do is to provide a big screen experience in high resolution at a very affordable price compared to a lot of our competitors. We offer even better specs in terms of a resolution brightness while our price is more affordable. Nice. And do you have another projector also or just a bunch of displays? Yeah. Let me grab this. So this is a much smaller projector than the other one. This is actually the M2E projector and it is portable. So it is designed to be a portable projector. You can throw this thing in your bag and it won't get damaged. It's got a cover over the lens. This is a 1080p projector with 1,000 LED lumens and 400 ANSI lumens. This is meant as a really cool entertainment piece. So it's got built-in, built-in Harman Kardon speakers and also has kind of the best complement of IO because we know that it's going to be using a lot of mobile devices. So that's why it's got USB-C, it's got a full-size USB, full-size HDMI, comes with a remote as well. And this one has Bluetooth in and out. Is that correct, Mia? Yeah. It has Bluetooth in and out. Yes. Okay. So yeah, if you wanted to say you were getting video from something like a streaming stick and you wanted that audio to go somewhere else, the Bluetooth output would allow you to run the audio to an external Bluetooth speaker. So if you didn't want to use the ones in here, you still have the ability to wirelessly send that to an audience. Nice. And then with Bluetooth, which I think could be the perfect match for some of these projectors is sometimes it's an audio sync issue or something like that. You have some way to make sure that it's perfect sync. That's a good question. Are you familiar with that, Mia? Yeah. Well, there's always going to be some issue, but ours is like standard Bluetooth 4.2. So it depends on the version. I cannot guarantee you like 100% all the Bluetooth would work, but just make sure that if you follow our version we have is Bluetooth 4.2. But one thing I was wondering is sometimes maybe there's few milliseconds of lag or delay in the sound, but maybe in your, hopefully in your settings, there's a way to adjust that. Maybe it's hopefully it's just perfect whenever people connect their Bluetooth speakers or Bluetooth headphones. Right. So you don't see the sound just a little bit after the mouth moving, hopefully. Hopefully. Yeah. And then you have a lot of monitors, PC monitors behind. Yes. So we have sort of a full complement of different monitors for different customers in different use cases. So let me get up here so I can show you this first one kind of get out of the way. This one here is a 34-inch ultra-wide monitor, in fact, slightly so you can see it a little bit. So this is a 34-inch ultra-wide monitor. This has a 3440 by 1440 resolution, which is very, very high for the 34-inch ultra-wide class. You usually don't see this until you get to more of the higher-end ultra-wides. But we expect a speed price of this below $400. So this will actually be a very interesting entrant into that marketplace because typically for this type of feature set you actually have to pay a lot more. It's also a full ergonomic monitor, so full height adjust is in there as well as tilt and swivel. It doesn't pivot because it's so big, but it does have all the other ergonomic complement with the stem. So I'm pretty excited about that. It's an IPS with a 420-dip brightness, so a very, very high-screen performance on that monitor. Let me adjust here just a little bit. It's a very immersive thing to have an ultra-wide, right, for gaming sometimes. Yes. Gaming, and this one is usually, if you want to do an immersive gaming ultra-wide, what you'll do is you'll curve it so that the screen is kind of going all the way around you. This one is a flat one, so it's a little bit more aimed at productivity. Side-by-side productivity. So you can have one window here and then a different window on the other side. That's sort of where the best use case for that monitor is. Moving down, we have this one right here. This is our VP3286-8K. This is a 8K monitor that will be coming out later in the year. It'll be an 8K monitor that is focused at sort of the professional that is doing a lot of high-end photo work. So it is 99% RGB, a full-color calibrated from the factory. And one really cool feature is it comes with this little cup. This will actually live on the base. There's a little spot for it to sit. And this is an early version of it. It'll change by the time it comes to production. But what this will do is it kind of lets you control the on-screen controls and displays. So if you need to change color modes or anything, very easy to control it. And then the other cool thing is this is actually a screen calibrator. So this thing, you put it on top of the screen, and any time you need to recalibrate your monitor, you have a calibrator that comes with the monitor and it just lives on the base. You never have to worry about keeping your monitor calibrated. We include it in the box with the monitor. Because 9, 2021, there's even more 8K cameras coming out, consumer 8K cameras, even smartphones can record 8K. Is it also suitable for the 8K video editing kind of market? Yes, it would be suitable for video editing as well. We actually have a companion series. So this is the 86 series. There will be a 76 series that's a little bit more focused to video production because that one targets the DCI-P3 color gamut, which is really very common work format gamut for video editing purposes. This one's more focused on the Adobe RGB, which is more for photography and print work, but absolutely can be used for that. So it could be great for color grading. Exactly, exactly. 32 inch is a very compressed 8K, but I mean, on the desktop? Yeah, absolutely. It'll have very, very high pixel density, absolutely. Do you have 8K projectors coming out? I'm not aware of any 8K projectors. Yeah, not at the moment. It really depends on taxing Schumann's chipset. Hopefully they announced something and then you have it later before CES 2022, right? Right, but hopefully we'll make a 4K projector more affordable and more popular. That'll be the first mission. Can you make the 4K projector the small size, the portable one? Or is it limited to 1080 for now? Well, for now, the one that we're showing you is 1080p. It will be kind of difficult to make a 4K in such a small, compact form to the reason it's because of brightness and also the thermal. Because if it's a 4K, but you don't have high brightness, it won't really justify if you can only, you know, it's a 4K, but you can only limit it to a certain very small size of the image screen then it won't justify the 4K. So I've always wanted to have a 4K Joy-Bee. Sorry, that's another company. Sorry, I know. Hey, actually, I worked with you on Joy-Bee before. Yeah, it was like 10 years ago. I did the Joy-Bee GP1 video. Yeah, I don't think they have a 4K version of a Joy-Bee. I think they still call it a GP something. They have GPV or I don't know, V1. Yeah, but I think we have better, we're better actually, Viewsonic is better in terms of the portable LED projector lineups. We have a more fuller lineups from 1080p to 480. So we incorporate a lot of the features that the other company, they don't have, such as the hard and common speakers. And also we have a lot of smart projectors, smart portable projectors. So if you are looking for a LED mini or Pico projectors, Viewsonic definitely has the most complete lineup. Do you have any with a Chromecast or Google TV? Not yet, right? Nice to have this stuff integrated. Not at the moment. So what you needed to work was the TV stick, the Google TV stick. Just connect one, yeah. Right, right. All right, it's like the little projector you have on your picture there, it'd be nice if it was 4K. Maybe eventually Texas Instruments will do some magic. Right, hopefully, yeah. Well, we'll see what happened in 2021 or 2022. And Ray, you have also other product launching there? Yeah, so kind of moving down the line now, this one is actually one that's already been on the market for a little while, but we brought it along because it is a very significant product for us. This is our TD1655 portable display. So this is a 15.6 inch portable monitor, IPS. It runs on USB Type-C primarily. Let me show you those ports right there. But it does also have an HDMI. So really nice productivity, especially on the go, if you need a really flexible work environment and you're trying to find an open space. Do people connect their smartphones to that? Like run Samsung DeX or the Huawei PC mode, they can run it directly from the smartphone, right? Yes, yes. It is up to the amount of power that the phone can supply. So there probably are some phones where if you try to connect the full screen to it, it can't give enough power, but we tried it with a pretty late model Galaxy and didn't have any issues and it was able to run. So it actually draws the power from the USB. There's no battery inside. Correct, there was no battery inside. However, in terms of power, we did include a 60 watt power adapter, which is a lot more than it needs. And the reason why is because with a 60 watt power adapter, you connect it to the wall, you connect the USB-C to this. This will only take about seven of those 60 watts and then the other watts will go to your laptop. So it'll actually charge your laptop just with a little small included charger that we include with this. And is there a price? Is a good affordable price for this device, for this display? Yes, we have two models. We have a touch and a non-touch. This one is touch, 10-point passive touch. This one is a 23 or sorry, this one is a 239.99 and then the non-touch is 179. All right, and it comes to the screen protector there. It does, right here on the front. This is magnetic. So it just, oops, it lined up correctly. That's my bad. And then it'll protect. Nice. All right. And moving down a little bit or did you have any other questions? No. Okay, moving down here, we have our Elite XG320U. This is our newest entrance to the Elite lineup. We're targeting a release around summertime. This is a 32 inch 4K with 144 Hertz refresh rate. And it's notable because it is the first, it will be the first ViewSonic monitor with HDMI 2.1. And this one will actually have dual 2.1 ports as well as a display port 1.4A. So this monitor is perfect for these next generation consoles that are coming around that support the 4K high refresh rate. So we expect to have full support of those as well when it comes out. And also on the gaming PC side, again, support up to past 120 goes all the way to 140. It is an HDR monitor as well. So 600 nit HDR is certified and supported. And this one is an AMD FreeSync premium pro monitor as well. So the adaptive sync technology is there as well. But because you are two HDMI 2.1, does I mean you also adapt to the other sync systems that the one from Nvidia and like it's part of the standard, like the variable, the referential that, or what you call it, the low latency? Yeah, so there's two standards there. The Nvidia one is G-Sync and that's typically supported on the display port ports. I believe G-Sync is supported on the display port. It's not supported on the HDMI. Is that correct Jason? Nope, we might have lost Jason again. That's all right. You typically won't get G-Sync on an HDMI whereas FreeSync you will. And then the other standard you were mentioning is HDMI variable refresh rate or VRR. That is part of the HDMI standard and that is supported by the next generation consoles and it shouldn't have any issues on here as well. Nice. And is it going to be a good price? We don't know. We're not ready to announce pricing at this point. We do believe that there have been some high refresh rate 4K monitors on the market that are very, very high end. We're definitely trying to undercut that pricing like one. What would be nice is if there's some nice cloud gaming systems that would support the whole 4K 144 Hertz. So people don't have to invest huge amounts of money in a huge desktop gaming machine to get the full quality of this display. Yeah, I agree. And I don't know of any. So the limitation there right now is not even really the service so much as I'm not aware of any streaming boxes from Google or anybody else that HDMI 2.1. But if they bring them out and they update them then sure there's no reason why they couldn't do that. Nice. And then the very last one we have there at the end that is the VG2440V. That is a 24 inch sort of business and work from home monitor that's notable because it has a built in camera on top. So we've had a webcam on monitor before but we wanted to bring updated one to the market a little bit better technology. So this one is the built in shutter. So if you're not working, you don't want to use the shutter and this camera can tilt forward and backwards by five degrees independently of the monitor. So you can tilt it down and up without having to adjust the monitor without having to mess up any of your perfect ergonomics on the monitor. And what's the resolution of the webcammer? The webcam is a 4 HD webcam. And so 1920 by 1080 and the monitor is also 1920 by 1080. So they kind of compliment each other. Nice. It'd be nice to have a 4K camera on top of the 4K display and the 8K camera on top of the 8K display. That might need to be the next generation then. It's quadruple. It's definitely something that would be good in this age of everybody video conferencing people. I mean, you're matching the resolution of the screen over there. And 1080p is actually better than many, it's better than all the laptop webcams, but... Yeah, yeah. A lot of the laptop webcams are still like around 720. So yeah, we think we'll get better visual fidelity with one of these. And like you say, we've had huge demands from education and enterprise that need this type of a solution. Nice. Awesome. So thanks a lot for showing all this cool stuff. The CES 2021 is interactive. It's online. I'm happy to do it. All right. Thank you. Thanks a lot. Thanks everybody. Thanks Mia and everybody for this video. Thank you. Just don't know if you need any more information.


Okay, we're going to continue where we left off on Friday. We were talking about addition to pi star, so addition to carbonyls. If you're not totally up with this, go back to your sophomore organic chemistry text and work every mechanism problem in the chapters on carbonyl addition, esters, ketones, aldehydes, amids, and that'll help you sort of get back into the swing of things. When we left off, we were talking about stereoselective additions. And the idea that stereogenic centers that are next to carbonyl groups affect which phase you prefer to add to in a kinetic and irreversible reaction. And this is the basis for modern stereoselective synthesis of polyketide natural products. So we talked about this Felkin-On analysis. And I'm just going to make a little point here that this is On's name. What's On's last name? It's Nguyen. So, but he, in his first paper, he wrote it the Vietnamese traditional way. His last name is Nguyen, not On, but we still call it the Felkin-On analysis. Okay, so whenever you do some sort of addition of a nucleophile, in this case, it's an allyl boronate. We'll talk more about these so you can understand the mechanism later. This stereogenic center here with this poorly rendered methyl group that's hashed influences which phase you add to that carbonyl. And I showed you this Felkin-On analysis for how to predict which phase is preferred. And what I said is rule number one, when there's not a polar group, there's a carbon atom here. This is very big, but it's because it's just a carbon atom, you don't consider a polar. As you want the nucleophile to attack the opposite, from the opposite phase of the big group. So I've drawn out two renderings, two Newman projections for what I would see if I stood right here and sort of viewed down this carbon-carbon bond. That's the Newman projection. And all I have to do is imagine as I stand and look down this carbon-carbon bond is imagine what would I see as I looked down that bond. So there's a hydrogen atom sticking here. And if I orient it so that the big group is going this way, I'll have a hydrogen here. And that other carbon is back and then I'll have a methyl group sticking up. And if I swing this big group all the way around so that it's on your left-hand side, then I'd have the hydrogen group going up and the medium-sized methyl group sticking down. So those are the two reactive confirmations that would fit with the nucleophile adding from either your left-hand side or the right-hand side. And so remember one of the conclusions or one of our analytical rules for the Falconon analysis is that the nucleophile attacks from a Berge-Dunnitz trajectory opposite the big group. And the Berge-Dunnitz trajectory over here opposite the big group would look like this. And we want to choose the depiction. We want to choose the trajectory that minimizes eclipsing interactions. And that's this one right here, H is small. As we're coming in, forming a bond, we don't want to be bumping into some big group here. We want to be bumping into this. So I'll just write better and worse. And of course when you look at this, this is a paper that was published about a week ago or something. I typed in, if you'd like to practice, type in quote Falconon into the ACS Journal's website and then start working problems in papers. There's paper, 500 hits came up. You have lots of chances to practice, to be good at it. Because I promise you on one of our exams, I will ask you this, I expect you to be so good at this that in seminar when somebody mentions the word Falconon, you know the prediction ahead of time. And you can see it gets very hard when you start to twist around the carbon backbone and translate things. That's where all the work is. Okay, so that's the Falconon analysis. In this paper, they claim the sole product was the one predicted by the Falconon rules. Okay, so let's come back and look at something that is not Falconon, it is a powerful source of stereo control. So this is, if it's not Falconon, it is usually this alternative. If it's not Falconon, it's giving you high selectivity. There are cases when you get exactly the opposite of the Falconon prediction and in almost all cases it's because of this, because there was chelation that was affecting the reaction. And Cram was the first one to predict that this was possible and his model still holds, we often call it Cram chelation control. So chelation control gives the opposite result that you would predict from the Falconon analysis. Let me give you an example of a substrate that is well designed to give high levels of chelation control and in this particular case there was oxygen at the alpha position, that's the polar group and according to the Falconon analysis, this oxygen atom will bias those two faces that the nucleophile wants to attack opposite from the opposite side of the polar group which is oxygen. The polar group is not hydrogen, the polar group is not this alkyl group, the polar group is this oxygen. But if you tried to use the Falconon analysis to predict which face you would get addition from if you added lithium aluminum hydride and so in this case the nucleophile is a nucleophilic aluminum hydride bond, aluminate hydride bond. If you tried to predict using the Falconon analysis, you'd get the incorrect prediction. So let me go ahead and draw out the products here and I'll give you some ratios. This group right here is called a benzyloxymethyl, some often called bomb, benzyloxymethyl, so I'll just write bomb here. And so the hydride that comes in can either come in from the top face and I'll write R1 over here for this other group and this is supposed to be an R2 down here and here's the other possible product where the hydrido group adds in from the back face and those are the two possibilities. And so in this case, the one that's favored significantly and this gives you a sense for what levels of stereoselectivity you can expect to see is you get about a 9 to 95 ratio favoring addition from the back face. And so why is that? That's the opposite of what you would predict if you had gone through all this trouble to draw out these two Falconon Newman projections. What's happening is that this happens to be a good, whenever you have oxygen at the alpha position, this turns out to be very good for chelation control. In other words, lithium wants eight electrons and so if you have a lithium cation floating around in there it loves to have oxygen lone pairs poking into that helping it to satisfy the octet rule. And in this particular case, you would expect just any alkoxy group at the alpha position to be good. This is even better because that extra oxygen can actually reach around and bind to the lithium through a three point chelation model. What that does is it forces this oxygen not to be 90 degrees to the carbonyl but it forces this oxygen to be in the same plane as the carbonyl. And so that now creates a face and this R2 group is now on the top face of that ring system, of the chelation ring system. So the nucleophile comes in and attacks from the back face. Okay, so top face is blocked and so the nucleophile comes which is the hydride group. All right, back face of this chelation ring here. So the top face is blocked. That's chelation control and it's, you find this occurring whenever you have, I'll show you some of the types of systems that give good results. So generally what you find, so what are the good chelating groups? In 99% of all cases it's some, well let me say 95% of all cases it's something like this. Where you have a simple alkyl, let me write alkyl here. Benzol would be one of the most common because it's easy to remove a benzol group. That's a common protecting group or perimethoxybenzol. So this would be good for chelation control because it allows some sort of a metal to grip those two, to be gripped by those two oxygen atoms. Here's what's not good, any kind of silo group and the more hindered the worse this will be. So I don't even want to draw anything. I'll just write not good here. There was recently a paper that was published that showed that there was a very specific case for diethyl zinc additions or alkyl zinc additions where you could have siloxy groups and it was so extraordinary and unusual that it was a JAX communication, just some special system where somebody finally got good chelation control with siloxy groups. You should as a general rule assume you are not going to get good chelation control if you have siloxy protecting groups at that position. You'll get Falcon on mode of addition. Okay, so what are some good metals for chelation control? And it's generally going to correlate with Lewis acidity. So titanium tetrachloride or any kind of titanium triflate. These are powerful oxophilic Lewis acids. I'll talk a little bit more about this in just a minute. So titanium, fantastic at being gripped by two metal atoms. Zinc, zinc chloride potentially. I would give you, you often see that used for chelation control zinc triflate, even better. Magnesium, magnesium perchlorate, magnesium bromide. So magnesium cations. They have a lot of partial positive charge. Probably, you can still see chelation control with lithium salts. So when you're using alkyl lithiums to add, oftentimes you'll, not every time, lithium, in this list lithium is the least good. So maybe I'll just put a pair of parentheses around that. But you can sometimes see a chelation control with lithium. Not always, but I would say more than 50% of the time. Okay, so how do you screw up chelation control? You compete with it. So for instance, if I were to add DMSO, you're not going to get any chelation control in DMSO. If you're using DMSO as your solvent. Why would any self-respecting metal want to coordinate with this lame system when it can coordinate to that ox? No metal will do that. Every metal will coordinate with the DMSO. If you take DMF, you're not going to get any chelation control. If you want to understand why the lone pairs on that oxygen or sodium nucleophilic draw the resonance structure of that using the nitrogen lone pair, and you'll see why that oxygen is so good at coordinating to metals. And undoubtedly, better than your substrate will coordinate to any metal. Alcoholic solvents seems pretty obvious to me why you wouldn't want to use that as a solvent for chelation control because your Lewis acid's going to coordinate to the alcohol lone pairs. And then the last, well, let me give you one more that would also be bad. This is dimethoxyethane, DME. And of course, that's got a built-in chelating group built into it, yeah. So let's say you do use one of these to see felkin on. Yes, would be the prediction as the default. Yep.  Sometimes you'll get good chelation control and sometimes you won't. But typically, if I wanted to dissuade chelation or, sorry, if I wanted to prefer chelation control, I'd use diethyl ether, just stay away from this. Sometimes you get good chelation control but those lone pairs are actually pretty good at coordinating to things. So if you have a choice, don't use THF if you want good chelation control. Okay, I want to give you a ranking series for Lewis acidity. Like if you have a choice to throw in some sort of a Lewis acid and next time I'll have to remember to bring in a racer or a used Kleenex which might have more effective chelation of ink. Thank you very much. Okay, I'm going to give you a series of numbers that came from this study. Somebody just used a simple NMR analysis to gauge the capacity for different Lewis acids to coordinate to oxygen and act as a Lewis acid. And what's the goal of having a Lewis acid coordinate to some sort of an oxygen atom? It's to make the oxygen more electropositive. It puts a formal charge on the oxygen. And if I draw the Lewis, sorry, the resonance structure for this, I can see why when I draw the Lewis structure, sorry, the resonance structure for this, I think I can see why nucleophiles would be more likely to add to this system. So that puts a formal positive here. There's another resonance structure that puts a formal positive charge where the carbonyl is. So I'm not going to draw that particular resonance structure. So you can see why when you coordinate a Lewis acid, it becomes faster for nucleophiles to attack either here or here. I'll just write or. So Lewis acids increase the reactivity of carbonyl compounds. That's just a general principle. Okay, somebody was very clever and you may have learned this in spectroscopy class already, but these protons at the beta position of enones are really shifted downfield in your NMR. They get shifted way over into the aromatic region because there's so much partial positive charge here in an enone. And it doesn't matter whether you have the Lewis acid there or not. They get shifted way far to downfield. And the better the Lewis acid, the more that proton gets shifted. It turns out you can simply look at the chemical shift of this proton and that tells you about Lewis acid strength. So somebody was very clever to do that simple study. So I'm going to give you a list of Lewis acids and the results that you get from that. What I'll give you is the thermodynamics of that process. And then from the NMR, I'll tell you about how it made the enone, the pi star system, more reactive. That's what I mean by lumo lowering. It's pi, I'll just call that pi star reactivity. The lowest unoccupied orbital in this is pi star. So let's take a, I'll draw out a series of Lewis acids for which there's data. Boron trichloride, of course, boron has an empty orbital. There's chlorines on there that are electronegative. Compare that to aluminum trichloride. And to boron trichloride, this is much more common than boron trichloride. Triethyl aluminum, you could say the same for trimethyl aluminum. And then the last Lewis acid I have numbers for is stanic tetrachloride. Okay, so if you look at the, I'm going to tell you about the enthalpies of binding here. And I'll ask you to note something that's different. One of these is not like the others. Well, I guess maybe two of these are not exactly like the others. So most of these are similar. And there's two kind of outliers here. And I can't believe, I'm going to put that, because I can't, sorry, I can't believe that that's positive. So let me just put this here. I think that's negative. And I wrote in my notes positive. And I'll check on that for you. Here's what's unusual about this. What they all predict for you is that these powerful Lewis acids enthalpically prefer to be bound to oxygen in a carbonyl, except for one, boron trifluoride. So there's an entropy component that's very similar for all of these, but enthalpically you would predict that most of the boron trifluoride would not be coordinated to your oxygen. BF3 spends only a fraction of the time, less than 0.1% of the time bound to the carbonyl. So if BF3 is going to be a good Lewis acid, in the small fraction of time that it is bound, it better be having a very powerful effect. So if you look at the LUMO lowering in these cases, and then the units are completely unimportant here, this is the most powerful Lewis acid on this list. And arbitrarily, this is measured in electron volts. Who cares? You just want to know what's big and what's small in terms of the effect. Aluminum trifluoride. It's not as powerful as BCL3. It's a longer bond is really what you're doing. You're dropping down to a lower row in the periodic table. Finally, we get down to BF3 even though it spends very little time bound to the carbonyl oxygen. When it is bound, it has a very powerful effect. And so, you know, it's somewhere in this range, even though it doesn't bind as tightly as a triethylaluminum, overall it has a very powerful Lewis acid effect. Triethylaluminum is down here. And then finally, that Stannic tetrachloride at 0.61. Now, there's one common Lewis acid that I don't have in this list and I don't know the numbers for that. My intuition is that Tickel 4 titanium tetrachloride fits somewhere around in this region and I don't know where. It's an extremely good Lewis acid and I don't know why they don't have numbers for that.  But of the things on this list, the tin is the least powerful based on those numbers that were measured. Okay, so Lewis acid massively increase the reactivity. They increase the amount of partial positive charge here. They lower the energy of the lumo. So, if you had some sort of a pi star lumo that you were looking to donate into with your nucleophile, here's my orbital energy diagram just as a way to look at that. So, you know, when you coordinate a Lewis acid, it's not just a charge effect, when you coordinate a Lewis acid, you lower the energy of the lumo by making the oxygen atom more electronegative. All the atoms in this pi system, every orbital associated with that oxygen atom gets lowered in energy. Okay, so Lewis acid, it's a cheap and easy way to increase the reactivity of your substrates and the rates of your side reactions. I'm going to draw a series of carbonyl groups, functional groups and we'll put some numbers on the rates of addition of typical nucleophiles. I want to start off by just drawing an important resonance structure for you so we can key in on the fact that donation by neighboring atoms slows the addition of external nucleophiles. So, here's what I mean. So, if you have a carbonyl group and you're interested in some nucleophile adding in, if you want to mess that up, then put another group here with lone pairs and you'll mess that up and you'll slow that down. Right, if you've already got a lone pair that is right next door, that is always donating in, how can this compete by colliding with that carbonyl carbon? I mean this is always there, it doesn't have to collide. Concentration doesn't matter, you always get effective donation. So, when you draw the resonance structure for this, you draw resonance structures when you believe that there's going to be effective donation. And there's another resonance structure that reminds you of why this is so reactive and that other resonance structure looks like this that reminds you of why carbonyls are so electrophilic on carbon. Okay, so there's an MO depiction for this. Any time you can draw donation of filled orbitals and done filled orbitals, there's an MO depiction. It's in the notes, but I'm not going to take the time to draw that out. What I want to do is I want to draw out relative rates of addition. So, we can see how this group, it's not always a lone pair by the way, how groups that are next door influence the rates of reaction in a quantitative way. And then I'll come back and draw that orbital depiction thing. I'm going to start off here with formaldehyde, extremely reactive, extremely reactive. There's no lone pairs on those hydrogen atoms. There's no pi bonds on the hydrogen atoms. There aren't even any sigma bonds sticking up on the hydrogen atoms that can donate over into the carbonyl group. There's nothing. This is about as reactive as you can get. So, that's the top of our reactivity list. And so, if I compare that to a ketone like acetaldehyde, where I've at least got a CH bond, three of them, but at any point in time, one, maybe depending on the alignments, two, but not so perfectly, but you've got these CH bonds that can donate into the antibonding orbital. And they help decrease the reactivity of this carbonyl group. And if I put two alkyl groups on there and make it something like acetone, I'm not going to draw the CH bonds, they're there. Acetone is less reactive. Ketones are less reactive than aldehydes. That's just a general principle. Ketones are less reactive than aldehydes. And then finally, not finally, but majorly, I can crush the reactivity of this by putting something with lone pairs on there. Let's have an oxygen with lone pairs. And if I really want to slow down the rates of addition of nucleophiles, let me put good lone pairs that are nucleophilic next door, like nitrogen, lone pairs, amids, that's why your proteins are made out of amid bonds. It keeps them from hydrolysing spontaneously. Water doesn't add spontaneously to the backbones of proteins because of that donation. So I'm going to compare all of these functional groups to an amid. I'll assign that a relative rate of one. And we're interested in rates of addition of hydroxide. So if that's a relative rate of one, turns out that formaldehyde has a relative rate of addition of hydroxide of 100 billion, 100 billion times faster for formaldehyde to react with hydroxide nucleophile, anion nucleophiles. And compared to this, formaldehyde, adding that one extra methyl group cost you a factor of 100 in rate. So acid aldehyde is 100 times slower than formaldehyde. That's the effect of one methyl group. That's the effect of the CH bonds on this methyl donating into the carbonyl. There's a steric effect. That's a smaller part of that. It's mainly the donation of the CH bonds into the carbonyl. I come down to acid. The second methyl group is pretty similar to the first. It costs another factor of 100. And then when we get down to esters, there's a bigger jump, not just a factor of 100. Now there's a 10 to the third. So acetone, ketones are about 1,000 times more reactive than an ester. If you have some complex substrate with 10 million atoms and a ketone and an ester, you should be able to react faster with the ketone. You should be able to add butyl grignard reagents or other things faster to ketones than esters. And amides, of course, you should expect them not to react, and that's why it's very common to protect amines with carbamate protecting groups. They put a carbonyl next to the lone pair. That resonance donation is very important. So it simultaneously reduces the electrophilicity of the carbonyl, and it also reduces the nucleophilicity of the nitrogen lone pair. What I don't have a number for but is also very common is alkoxide, anions, I mean there's always something coordinated to that, sodium or lithium. Those are less reactive than amides, and I don't have a number. I'll simply say less than 1 on this reactivity list. Okay, so again, let me just come back to this. Like why is an ester so unreactive? What is this picture telling us, this resonance picture? If I have a lone pair donating into a carbonyl group like an ester, so let me dissect out this ester here, and I'll draw out these pieces of that puzzle. So let me start off by drawing the donor group here. If I want to think about what's the effect on the reactivity on this pi star system? What's the effect of this lone pair nearby? So let me draw out an orbital energy diagram to think about the interaction of this lone pair with this pi star system. So we can try to think about using orbitals and some sort of orbital energy diagram, what's the effect? So unfilled orbitals are higher in energy than filled orbitals. Here's my pi star for a carbonyl group. So here's my two pieces. Here's the carbonyl pi star. Here's the nucleophilic, I've sort of flipped it around there. So if I wanted to think about the interaction of these two pieces, if I mix two orbitals, I get two orbitals out. I get one orbital that's lower in energy and one orbital that's higher in energy. And what's the symmetry of these two new orbitals that I get out? They're pi-like, right? That's what I drew here. I drew pi. So let me label them pi something. So I get two new orbitals out. One's an antibonding orbital. One is filled. And so here's the little interaction diagram. And this is filled, the bottom orbital. What it tells me, right? Look at the orbitals that I get out. It's when I have donation like this. If I have donation where this lone pair donates into pi star, the system actually will now have a higher pi star. My MO diagram is telling me that it is now harder to add to an ester pi star because of that donation. Now, I don't expect you to draw these diagrams, right? I just expect you to look at this and say, oh yeah, there's lone pairs donating in. And that's why esters are unreactive. But if you ever need to, you can draw diagrams to back up your thinking or you sort of dissect this into a set of orbital interactions each with an associated energy. So four dimethylamino pyridine is a very common catalyst for organic reactions. So here's the structure of DMAP. There's a dimethylamino group at the four position of this pyridine ring. And Wolfgang Steglich was studying something called the Dock and West Reaction. Thirty years ago, this has nothing to do with the Dock and West Reaction. And when he was doing those very strange reactions of amino acids, he realized, hey, this type of catalyst has an extraordinary effect. Maybe I can use it for other reactions of carbonyl groups. And so what he showed is that if you take a typical acylation reaction and it's not fast enough for you, you can simply add 10 mole percent of this amine catalyst. Not triethylamine, not just pyridine, but DMAP. And when you add that, you'll isolate that alcohol. You'll perform acyl transfer reactions about 10,000 times faster. Just that 10 mole percent, of course, if you had 20 mole percent, it'll be 2 times 10 to the fourth faster. If you had 10 times more DMAP, you should get 10 to the fifth faster. So just that small amount of DMAP can give you phenomenal rate accelerations. And what we now know is that these reactions occur because DMAP is nucleophilic, and I'm not going to show all the arrow pushing for this. It attacks the carbonyl group faster than the crummy alcohol substrate. But what you could not have predicted ahead of time is that this intermediate, this acyl pyridinium intermediate, is more reactive than the original anhydride. And this is also true for acycloides. It's now faster to attack that carbonyl now that it's an acyl pyridinium. There's now this charged leaving group that's right next door that gives it more calomic positive potential, more of a positive partial positive charge on the carbonyl carbonyl. So this is the mechanism for DMAP catalysis.  So it's a general principle of catalysis. So we call this nucleophilic catalysis because the DMAP had to act as a nucleophile and attack the carbonyl first. So if you look inside the ribosome, it's a massive structure, it's got a molecular weight on the order of 40 million, thousands of residues in there. And there is a single base residue, a single nucleotide in the ribosome. So in the mammalian ribosome, it's A246. Right, there's thousands of adenines in there. That's adenine 2486, 2486. All the ribosome for all that size boils down to this. The whole ribosome is there to position this one base, this one nucleotide, this one base, this one atom and that one lone pair next to two key functional groups, an ester and an amine nucleophile. So inside the active site of the ribosome, you've got an RNA ester with an amino acid hanging off the end so it's just an ester, it's nothing special about. And then you have your growing protein chain which is just an amine and the whole ribosome is there to catalyze this acylation reaction where you transfer this acyl group of a new amino acid onto the end terminus of a growing protein chain. And so in the end, you get a new peptide bond. But I'm not going to show you the whole amino acid, it doesn't matter, the point is that this is just, the whole ribosome boils down to a single lone pair. And so what's the mechanism for this in the active? You know, I draw this up here and then you look down here and it's, it kind of looks similar. You know, just like for DMAP you might think, well, maybe this lone pair here is donating and I can draw a resonance structure where I enhance the nucleophilicity of that nitrogen. Maybe that's what the ribosome is really doing. Maybe that's the whole purpose of this particular adenine base in the ribosome. It turns out that's not the role and you could never have predicted this ahead of time. It turns out that that one single lone pair in the ribosome is just there for this. It is just there to help the ribosome deprotonate this intermediate. After the protein amine attacks that ester, you generate this zwitterionic intermediate. And as soon as you pull this proton off, there's now a lone pair that can help push out the TRNA leaving group. And you can't push out that TRNA leaving group until you generate a lone pair on nitrogen. It's too slow. So there's two different very similar things here. There's some, there's just plain DMAP that goes through nucleophilic catalysis, right? You could imagine this adding to the acyl group and generating an acyl periodinium salt. But then there's also base catalysis. And so both of these are well-precedented in the literature. How do you tell the difference when you run a reaction? Whether something is going through nucleophilic catalysis or going through this kind of base catalysis. No, the adenine 2486 inside the ribosome does not attack the carbonyl group. It's just after this nitrogen attacks, it generates this intermediate. And then the key step in peptide bond formation is for the, this lone pair to pull this proton off this tetrahedral intermediate. That's the step that the ribosome is catalyzing that leads to rate acceleration.  Okay, so let's talk about a simple test here. To distinguish these two, I heard John Browman who was one of the three editors for Science Magazine referred to this as the most brilliant experiment he had ever seen in his life. And maybe he was being overly, it's an experiment to distinguish these two possible mechanistic pathways.  These are just tiny, tiny polystyrene beads. These are the same types of solid phase resins you use for ion exchange, for peptide synthesis, for some types of DNA synthesis. And so what I want you to imagine is taking two pools of resin, two piles of resin here of beads. And in one pile of beads, I've got attached to that an a-seal derivative.  So that turns out to be a good leaving group, this nitrofenolate. And he found some way to hook this up to the plastic beads. And so what he wanted to test, what he wanted to test would is how quickly, if I have another pile of beads and I mix these beads all together, if I have one pile of beads, how quickly would this a-seal group get transferred to make a new amide bond? And what he showed is that if you simply mix the beads in solution, there's no transfer. The a-seal groups never get transferred over here. If you physically take the beads and mix them together and then grind them, you still don't get any amide bond formation. But then what he showed is if you take simple catalysts like DMAP or emidazole, which is the side chain of histidine, which has a very similar effect to DMAP, what he showed is that as soon as he added emidazole to solutions that had these two sets of beads floating around, that the emidazole would come in and pick up this group, fly around to an a-seal emidazoleum intermediate and transfer the a-seal groups to the other beads. In other words, you've got two different phases here, two solid phases that don't react. But as soon as you have a soluble species that's capable of nucleophilic catalysis in there, that that leads to a chemical reaction. So here's the end product of the reaction. And this reaction proceeds through an a-seal, emidazoleum intermediate. It works because the emidazole attacks and then pops out the leaving group and then it floats around carrying this a-seal group. And those a-seal, emidazoleum intermediates can float around between the beads and then come and be attacked by the nitrogen lone pairs. So it's called the three-phrase test and it is proof that it's not just the basicity of the medium. It's not just the basicity of the solvent that matters. You have to have some group that's capable of nucleophilic catalysis that can literally pick up groups and move them to other beads. And so it's an easy, I say it's easy to test. You actually have to synthesize the two types of polymer supports. But this is what allows this transfer to occur. Okay, so that's a three-phase, the three-phase test can distinguish nucleophilic catalysis from base catalysis. Okay, so I want to look at electronic effects and strain effects on the reactivity of carbonyl groups. And so what I have numbers for is this equilibrium where water is acting as a nucleophile. So yeah, that's not a very interesting nucleophile but that's what I have numbers for. I'm going to draw my carbonyl group in this resonance depiction form. Because I want, you can think of carbonyl in your mind. But that's a carbonyl group. I'm just drawing the charge-separated resonance structure. And because it reminds us that we're interested in reactions in which a nucleophile attacks a carbonyl. So if you look at water as the nucleophile, it turns out it's easy to get numbers for this where water acts as a nucleophile. And it's more than one step in the mechanism. That doesn't matter. But we're interested in the equilibrium constant for formation, this is called a hydrate for formation of this nucleophilic adduct called a hydrate. Okay, so let's look at the equilibrium constant as we change the R groups on this system. And I'm going to compare this to a molecule that you ought to have an intuition for and that's acetone. It's like the prototype ketone, the simplest ketone you can have. So if we look at the equilibrium constant for addition to water, it's not, I mean it can't be zero, but it's not zero. I mean there's some of the hydrate when you just get a bottle of acetone that's wet. There's hydrate in there. If you just take acetone right out of the bottle, if it's not dried in some way, you might expect to see a little smidgen of OH stretches in your IR spectrum. Okay, so what happens as we replace this with groups that are not as good at donating? So here's what I have numbers for. What would happen if I replace one of the methyl groups of acetone with a carbonyl group? This isn't as nucleophilic anymore. The CH's here donate into the carbonyl and make it harder for water to add. But a pi system here is not as nucleophilic. What you see, and there's also this sort of dipole effect which destabilizes this di carbonyl structure, it turns out that water, the hydrate form of that, is much more preferred. So now it's like a, I don't know, like a 6 to 10 ratio, what I don't even know what this is, 0.6 equilibrium constant, a 6 to 10 ratio of hydrate, 6 out of every 16 molecules now exists as the hydrate. So this is a better donor. This CH bond is a better donor in a way than this pi bond, and there's this dipole thing which is opposing. If I go to acid aldehyde, it's very hard to work with acid aldehyde.  It's very volatile, it's hard to get it dry, and if you don't get it dry, it exists as the hydrate in a 1 to 1 ratio if there's water present. If you don't have CH bonds here on this side to donate in, it turns out that carbonyl is very reactive even with water. Then we get formaldehyde. Remember the super reactivity of formaldehyde? There's very little formaldehyde in formaldehyde.  So here's what you buy when you buy formaldehyde, you buy this infimic polymer called paraformaldehyde in which one carbonyl group on one formaldehyde is attacked, another carbonyl group.  Alternatively, you buy solutions in water or methanol. Methanolic solution is called formalin, and those exist as adducts. If you really want to soup up the reactivity of a ketone, put trifluoromethyl groups on there. Those are awful, awful donors. You can imagine that carbon fluorine bonds have no nucleophilicity to them. There's no nucleophilicity to these carbon nucleophones. Those aren't going to attack anything ever. So there's very little donation here, and at the same time that there's very little donation by this carbon fluorine bond, fluorine is also very electronegative. It's the most electronegative atom in the periodic table. And so that increases the partial positive charge there. So if you look at the effect here, this is all hydrate. If there's any water around, it'll sponge out the water and exist as this hydrate diol. There's a drug called lubeprostone. Some of them I don't know that I think you can guess what lubeprostone is, but it helps to lubricate your gastrointestinal tract. That's not the important point. But lubeprostone exists like this. Let me try to draw out the structure for lubeprostone. Lubeprostone is actually a hydroxy ketone. But the medicinal chemists who designed this were very clever. They put this, so this is not the whole structure for lubeprostone, but they were very clever to put a diphthoromethal group on one side of the carbonyl. And guess what that does to the equilibrium for cyclization? If you don't have those two fluorine groups on there, then you get more of this free open chain form. But once you put that diphthoromethal group in there, the equilibrium very heavily lies on the side. Of this closed chain form. And that's the active species that binds to whatever receptor, some ion channel, I think inside of cells. And so that's just somebody using this simple little trick of putting carbon fluorine bonds instead of carbon age bonds. Okay, so let's take a look at the effects of strain. Cyclopropanone, you can buy cyclopropanone, you can't buy cyclopropanone as cyclopropanone, but you can buy hydrates of cyclopropanone or ethoxyacetals, hemiacetals. Of cyclopropanone, there's nothing that exotic about that. It massively prefers to exist as the adduct and it massively does not want to exist as the ketone. And this is the effect of ring strain. If you look at the intrinsic preference for a hydrate for a carbon atom that has four substituents, this wants to be 109 degrees. A carbon with four substituents. If you look at a carbon atom that has three substituents like this, that carbonyl group wants to be 120 degrees. And in this case, because it's a cyclopropane ring, it doesn't get to be either. The fact is that when you've got three carbons bonded to each other, all those angles are 60 degrees and all these angles are 60 degrees. So it's basically a matter of which sucks less. You don't get to be 60.  At least 109 is closer to 60 than 120. And so cyclopropanone, again, you can't buy that. You can only buy acetals of cyclopropanone. They're not happy. Okay, so I'm going to go ahead and stop right there. And when we come back, I'll talk about various ring sizes for ketones, cyclopentanone, cyclohexanone versus free acetone. And then we'll talk about some other types of pi star systems.