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Synthesis 2001(9): 1321-1326
DOI: 10.1055/s-2001-15220
PAPER
© Georg Thieme Verlag Stuttgart · New York

Highly Regioselective and Stereoselective Radical Addition of p-TsBr to Substituted Terminal Allenes and Their Nucleophilic Substitutions: Synthesis of α,β-Unsaturated Sulfones

Suk-Ku Kang*, Ho-Won Seo, Young-Hwan Ha
Department of Chemistry and BK-21 School of Molecular Science, Sungkyunkwan University, Suwon 440-746, Korea
Fax: +82(031)2907079; e-Mail: skkang@chem.skku.ac.kr;
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Publication History

Received 8 February 2001
Publication Date:
24 September 2004 (online)

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Abstract

Regioselective and stereoselective radical addition of p-TsBr to substituted allenes in the presence of a catalytic amount of AIBN afforded tosyl-substituted primary (E)-allylic bromides as the sole products. The nucleophilic substitution of the resulting allylic bromides to give substituted α,β-unsaturated sulfone derivatives is described.

Keywords

allenes - radical reactions - sulfones - nucleophilic substitutions

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7

The E stereochemistry of 3a, 3b, 3d, and 3e was confirmed by 1H NMR NOE experiments (Figure).

Figure