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Article

Fe(0)-Mediated Synthesis of Tri- and Tetra-Substituted Olefins from Carbonyls: An Environmentally Friendly Alternative to Cr(II)

Supporting Info

J. R. Falck,*^† Romain Bejot,^‡ Deb K. Barma,^† Anish Bandyopadhyay,^† Suju Joseph,^† and Charles Mioskowski*^‡;

Department of Biochemistry, University of Texas Southwestern Medical Center, Dallas, Texas 75390, and Laboratoire de Synthse Bio-Organique, UMR 7175-LC1, Facult de Pharmacie, Universit Louis Pasteur, 74 Route du Rhin, BP 24, 67 401 Illkirch, France

J. Org. Chem., 2006, 71 (21), pp 8178–8182

DOI: 10.1021/jo061445u

Publication Date (Web): September 13, 2006

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 Texas Southwestern Medical Center. Tel: 214−648−2406. Fax: 214−648−6455.

‡

Université Louis Pasteur. Fax: (+33) 3−9024−4306.

, j.falck@utsouthwestern.edu, ; , mioskow@aspirine.u-strasbg.fr

Abstract

Fe(0) was investigated as a cost-effective, environmentally friendly alternative to Cr(II) for the olefination of carbonyls by activated polyhalides. In many instances, Fe(0) was equivalent or superior to Cr(II). Notably, Fe(0), but not Cr(II), proved compatible with a wide range of functionality, inter alia, unprotected phenol, aryl nitro, carboxylic acid, and alkyl nitrile. A surprising reversal of stereoselectivity for aldehydes versus ketones was observed using both metals. The resultant α-halo-α,β-unsaturated or α,β-unsaturated carboxylic acids, esters, and nitriles are common structural elements in numerous compounds of interest as well as key intermediates in the preparation of other functionality.

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