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Title:Studies in Asymmetric Catalysis: Lewis Base Catalyzed, Enantioselective Addition of Trimethylsilyl Cyanide, Trimethylsilyltrifluoromethane, and Glycolate-Derived Silyl Ketene Acetals to Aldehydes
Author(s):Chung, Won-Jin
Doctoral Committee Chair(s):Denmark, Scott E.
Department / Program:Chemistry
Discipline:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Degree:Ph.D.
Genre:Dissertation
Subject(s):Chemistry, Organic
Abstract:A catalytic system involving silicon tetrachloride and a chiral, Lewis basic bisphosphoramide catalyst is effective for the addition of glycolate-derived silyl ketene acetals to aldehydes. The sense of diastereoselectivty could be modulated by changing the size of the substituents on the silyl ketene acetals. In general, the trimethylsilyl ketene acetals derived from methyl glycolates with a large protecting group on alpha-oxygen provide enantiomerically enriched alpha,beta-dihydroxy esters with high syn-diastereoselectivity, whereas the tert-butyldimethylsilyl ketene acetals derived from bulky esters of alpha-methoxy acetic acid provide enantiomerically enriched alpha,beta-dihydroxy esters with high anti-diastereoselecitvity. The observed diastereoselectivity and reactivity could be rationalized by the analysis of six open transition states with the aid of computational calculation.
Issue Date:2008
Type:Text
Language:English
Description:418 p.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2008.
URI:http://hdl.handle.net/2142/84290
Other Identifier(s):(MiAaPQ)AAI3314748
Date Available in IDEALS:2015-09-25
Date Deposited:2008


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