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Dimethyl Sulfoxide Mediated Elimination Reactions in 3-Aryl 2,3-Dihalopropanoates: Scope and Mechanistic Insights

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Wei Li,*^† Jianchang Li,^† Melissa Lin,^‡ Sumrit Wacharasindhu,^‡ Keiko Tabei,^‡ and Tarek S. Mansour^‡

Chemical and Screening Sciences, Wyeth Research, 200 Cambridge Park Drive, Cambridge, Massachusetts 02140, and Chemical and Screening Sciences, Wyeth Research, 401 North Middletown Road, Pearl River, New York 10965

J. Org. Chem., 2007, 72 (16), pp 6016–6021

DOI: 10.1021/jo070217c

Publication Date (Web): July 12, 2007

Section:

Aliphatic Compounds

Abstract

Dimethyl sulfoxide (DMSO) efficiently causes the reductive elimination of 3-aryl 2,3-dibromopropanoates to cinnamates with good yield. With 3-phenyl 2,3-dihalopropanoates, debromination is the major pathway providing 3-phenylacrylate derivatives in high yields, whereas dehydrobromination is a competing pathway with thiophene derivatives. ¹H NMR, ⁸¹Br NMR, and MS techniques indicated the formation of brominated-DMSO, MeBr, and HBr as byproducts in this transformation with no evidence for the formation of Br₂. The dual role of DMSO as a nucleophile and bromine scavenger accounts for the products formed in this reaction.

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This article has been cited by 3 ACS Journal articles (3 most recent appear below).

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Mechanistic Pathways in CF₃COOH-Mediated Deacetalization Reactions
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  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
Preparation of α-Haloacrylate Derivatives via Dimethyl Sulfoxide-Mediated Selective Dehydrohalogenation
Wei Li, Jianchang Li, Zhao-Kui Wan, Junjun Wu, and Walter Massefski
Organic Letters2007 9 (22), 4607-4610
- Preparation of α-Haloacrylate Derivatives via Dimethyl Sulfoxide-Mediated Selective Dehydrohalogenation
  Wei Li, Jianchang Li, Zhao-Kui Wan, Junjun Wu, and Walter Massefski
  Organic Letters2007 9 (22), 4607-4610
  Dimethyl sulfoxide causes α,β-dihalopropanoate derivatives to undergo efficient, selective dehydrohalogenation to form α-haloacrylate analogues. A variety of α-halo Michael acceptors were prepared in dimethyl sulfoxide under mild, base-free conditions, ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links