Catalytic, enantioselective aldol additions to ketones.
Catalytic, enantioselective additions of a trichlorosilyl ketene acetal to ketones have been demonstrated. The trichlorosilyl enolate of methyl acetate undergoes a rapid and high-yielding aldol addition to a wide range of ketones (aromatic, olefinic, acetylenic, aliphatic) in the presence of a catalytic amount of pyridine N-oxide. Moreover, in the presence of a catalytic amount (10 mol %) of a chiral bispyridine bis N-oxide (possessing both axial and central chiral elements) the aldol addition takes place again in excellent yield and with good stereoselectivity. The enantioselectivities of the additions are highly variable (7-86% ee) and are strongly dependent on the structure of the ketone acceptor. Aromatic methyl ketones gave the highest selectivity, whereas olefinic ketones were the least selective.
Denmark
Scott E
SE
Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801, USA. denmark@scs.uiuc.edu
Fan
Yu
Y