Mechanisms of the α,α-diphenylprolinol trimethylsilyl ether-catalyzed enantioselective aza-Michael reaction

Depending on the nature of the aza-Michael donor, the C-N bond formation in the α,α-diphenylprolinol trimethylsilyl ether-catalyzed aza-Michael reactions was found to proceed via either (i) an iminol intermediate in a stepwise reaction, or (ii) a concerted reaction. This is contrary to the commonly proposed iminium mechanism for organocatalyst-catalyzed aza-Michael reactions. The iminol intermediate is formed from the reaction between the catalyst and the amine (Michael donor). These proposed mechanisms are able to account for the experimentally observed product enantioselectivity.

(S)-Cat1-catalyzed aza-Michael reactions: same catalyst, different reaction mechanisms!