Lewis base catalyzed addition of trimethylsilyl cyanide to aldehydes.
A variety of achiral Lewis bases were found to catalyze the addition of TMSCN to the aldehydes. Among them, phosphines and amines were the most efficient catalysts. In addition, several chiral amines and phosphines were examined in a catalytic, asymmetric addition of TMSCN to benzaldehyde albeit with low enantioselectivity. A mechanistic study revealed that the reaction was first order in aldehyde, first order in Lewis base, and zeroth order in TMSCN, suggesting the complex formation of TMSCN and Lewis base formation of complex i. However, there are at least two possible scenarios for this catalytic process, and in view of the low selectivities observed, it is not clear which mechanism is operative.
Denmark
Scott E
SE
Department of Chemistry, Roger Adams Laboratory, University of Illinois, Urbana, Illinois 61801, USA. denmark@scs.uiuc.edu
Chung
Won-Jin
WJ