SmI2-Promoted Reformatsky-Type Coupling Reactions in Exceptionally Hindered Contexts

Org. Lett., 10 (6), 1291 -1294, 2008. 10.1021/ol800099a S1523-7060(80)00099-5
Web Release Date: February 27, 2008

SmI₂-Promoted Reformatsky-Type Coupling Reactions in Exceptionally Hindered Contexts

Brian A. Sparling, Ryan M. Moslin, and Timothy F. Jamison*

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139

tfj@mit.edu

Received January 22, 2008

Abstract:

Highly substituted, very hindered enones were synthesized using a two-step procedure that utilizes a diiodosamarium-promoted Reformatsky-type coupling and dehydration using Martin sulfurane. Both

-chloro- and

-bromoketones were coupled with a variety of carbonyl nucleophiles to form the intermediate

-hydroxyketones, occurring with excellent diastereoselectivity, favoring the syn isomer (R¹ = Me). This technique complements other methods and enables the preparation of enones outside of the scope of current olefination methodology.

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