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The Reactivity of Epoxides with Lithium 2,2,6,6-Tetramethylpiperidide in Combination with Organolithiums or Grignard Reagents

Supporting Info

David M. Hodgson,*^† Matthew J. Fleming,^† and Steven J. Stanway^‡

Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford OX1 3TA, United Kingdom, and Neurology & GI Centre of Excellence for Drug Discovery, GlaxoSmithKline, New Frontiers Science Park, Third Avenue, Harlow, Essex CM19 5AW, United Kingdom

J. Org. Chem., 2007, 72 (13), pp 4763–4773

DOI: 10.1021/jo070291v

Publication Date (Web): May 26, 2007

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

†

University of Oxford.

‡

GlaxoSmithKline.

, david.hodgson@chem.ox.ac.uk

Abstract

The scope and limitations of lithium 2,2,6,6-tetramethylpiperidide (LTMP)-modified reductive alkylation of epoxides is detailed. A variety of organolithiums are added to terminal and 2,2-disubstituted epoxides in the presence of LTMP to generate alkenes in a completely regio- and highly stereoselective manner. Arylated alkenes, dienes, allylsilanes, and enynes are accessed using this procedure. The methodology is applied in the synthesis of the roller leaf moth pheromone, (3E,5Z)-dodecadienyl acetate. The corresponding reaction without LTMP has also been examined, and a study using deuterated epoxides provides insight into the mechanism. In the presence of LTMP, Grignard reagents are also shown to produce E-alkenes directly from epoxides.

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