J. Am. Chem. Soc., 126 (13), 4245 -4255, 2004. 10.1021/ja039046t S0002-7863(03)09046-2
Web Release Date: March 13, 2004

Copyright © 2004 American Chemical Society

Catalytic, Asymmetric -Chlorination of Acid Halides

Stefan France, Harald Wack, Andrew E. Taggi, Ahmed M. Hafez, Ty R. Wagerle, Meha H. Shah, Crystal L. Dusich, and Thomas Lectka*

Contribution from the Department of Chemistry, New Chemistry Building, Johns Hopkins University, 3400 North Charles Street, Baltimore, Maryland 21218

lectka@jhu.edu

Received October 14, 2003

Abstract:

We present a full account of a tandem catalytic, asymmetric chlorination/esterification process that produces highly optically enriched -chloroesters from inexpensive, commercially available acid halides using cinchona alkaloid derivatives as catalysts and polychlorinated quinones as halogenating agents. We have performed kinetics and control experiments to investigate the reaction mechanism and establish conditions under which the reactions can be best performed. We have developed NaH and NaHCO3 shuttle base systems as the easiest and most cost-effective ways of conducting the reactions, rendering the methodology economically competitive with known chiral halogenation procedures. We have also demonstrated the utility of our reactions by converting the products to synthetically useful derivatives.

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