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Synthesis 2020; 52(10): 1544-1560
DOI: 10.1055/s-0039-1690826
paper
© Georg Thieme Verlag Stuttgart · New York

Chelation and Stereodirecting Group Effects on Regio- and Diastereoselective Samarium(II)-Water Allylic Benzoate Reductions

Trevor F. Stockdale
,
Michael A. Leitch
,
Gregory W. O’Neil∗
Department of Chemistry, Western Washington University, 516 High Street, Bellingham, WA 98225, USA   Email: oneilg@wwu.edu
› Author AffiliationsNational Science Foundation (CHE-1760918)
Further Information

Publication History

Received: 31 December 2019

Accepted after revision: 28 January 2020

Publication Date:
20 February 2020 (online)

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Abstract

SmI2(H2O)n reductions of allylic benzoates adjacent to a trisubstituted alkene occur in high yields with complete regioselectivity and good diastereoselectivity (up to 90:10) for substrates containing properly positioned stereodirecting- and chelating groups. The outcome of these reactions can be rationalized by ring conformation considerations of a proposed chelated organosamarium intermediate, and a mechanism involving intramolecular protonation by a samarium-bound water.

Key words

samarium - reduction - diastereoselective - regioselective - chelation

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0039-1690826.
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