 "Syn"-hyrdoborylated indolines are obtained.Borylation of S-H bonds in thiols by a dehydrogenative process has also been observed.Alcohols and amines such as tert-Butanol and tert-Butylamine form stable products that prevent catalysis due to a strong π-bond between the N/O atom’s lone pair and boron, whereas the same is not true for thiols, thus allowing for successful catalysis.