Enantioselective desymmetrization of meso-epoxides with anilines catalyzed by polymeric and monomeric Ti(IV) salen complexes

The active catalysts for the enantioselective ring opening (ARO) of meso‐stilbene oxide, cis‐butene oxide, cyclohexene oxide, cyclopentene oxide, and cyclooctene oxide with various substituted anilines were generated in situ by the reaction of Ti(OiPr)4 with poly‐[(R,R)‐N,N′‐bis‐{3‐(1,1‐dimethylethyl)‐5‐methylene salicylidene} cyclohexane‐1,2‐diamine]‐1 and (1R,2R)‐N,N′‐bis[3,5‐di(tert‐butyl)salicylidene] cyclohexane‐1,2‐diamine‐2. These catalysts in the presence of nonracemic imine as an additive provided β‐amino alcohol in excellent yield (99%) and chiral purity (enantiomeric excess (ee) up to 99%) for the ARO of meso‐stilbene oxide with aniline. The same protocol was less effective for the ARO of cyclic epoxides; however, when triphenylphosphine was used as an additive, there was a significant improvement in catalyst performance for the ARO of cyclohexene oxide (yield, 85–90%; ee, 63–67%). Both in situ generated polymeric and monomeric catalysts performed in a similar manner except that the polymeric catalyst Ti(IV)‐1 was more active and recycled several times with retention of enantioselectivity when compared with the monomeric catalyst Ti(IV)‐2, which was nonrecyclable. Chirality, 2011. © 2010 Wiley‐Liss, Inc.