ja027468h_si_002.cif (12.68 kB)

Broad-Spectrum Enantioselective Diels−Alder Catalysis by Chiral, Cationic Oxazaborolidines

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posted on 07.08.2002, 00:00 by Do Hyun Ryu, Thomas W. Lee, E. J. Corey
The cationic chiral Lewis acids 1 and 2, generated by triflic acid protonation of the corresponding neutral oxazaborolidines, serve as excellent catalysts for Diels−Alder addition of cyclopentadiene to a wide variety of dienophiles. Adducts have been obtained in excellent yield and enantioselectivity from α,β-unsaturated esters, lactones, and cyclic ketones. The absolute facial selectivity for each of these substrates follows a common pattern which differs from that observed with α,β-enals. The different reaction channels can be understood in terms of pathways via complexes 3 (for α,β-enals) and 4 (for α,β-enones and esters).