Lewis Base Activation of Lewis Acids. Addition of Silyl Ketene Acetals to Aldehydes

Lewis Base Activation of Lewis Acids. Addition of Silyl Ketene Acetals to Aldehydes

The weak Lewis acid silicon tetrachloride can be activated by catalytic amounts of the chiral bisphosphoramide (R,R)-3 to form a highly reactive, chiral trichlorosilyl cation which is an extremely effective promoter of aldol addition reactions between aldehydes and silyl ketene acetals. The tert-but...

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Veröffentlicht in:Journal of the American Chemical Society 2002-11, Vol.124 (45), p.13405-13407
Hauptverfasser: Denmark, Scott E, Wynn, Thomas, Beutner, Gregory L
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Exact sciences and technology
Organic chemistry
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container_issue 45
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container_title Journal of the American Chemical Society
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creator Denmark, Scott E
Wynn, Thomas
Beutner, Gregory L
description The weak Lewis acid silicon tetrachloride can be activated by catalytic amounts of the chiral bisphosphoramide (R,R)-3 to form a highly reactive, chiral trichlorosilyl cation which is an extremely effective promoter of aldol addition reactions between aldehydes and silyl ketene acetals. The tert-butyldimethylsilyl ketene acetal of methyl acetate adds nearly instantaneously to aromatic and olefinic aldehydes as well as aliphatic aldehydes (albeit more slowly) with excellent enantioselectivity. The homologous tert-butyldimethylsilyl ketene acetal of tert-butyl propanoate adds with nearly exclusive anti diastereoselectivity to a similar range of aldehydes also with excellent enantioselectivity. The origin of the slower reaction rate with aliphatic aldehydes is revealed to be the formation of chlorosilyl ether adducts.
doi_str_mv 10.1021/ja0282947
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Organic chemistry
title Lewis Base Activation of Lewis Acids. Addition of Silyl Ketene Acetals to Aldehydes
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