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Synlett 2007(8): 1314-1316  
DOI: 10.1055/s-2007-977454
LETTER
© Georg Thieme Verlag Stuttgart · New York

Rhodium-Catalyzed Reaction of Diazoacetates, Thiols and Azodicarboxylates: An Unusual 1,2-Aza Shift from a Sulfonium Ylide

Haoxi Huanga,b,c, Wenhao Hu*a
a Department of Chemistry, East China Normal University, Shanghai 200062, P. R. of China
Fax: +86(21)62233176; e-Mail: whu@chem.ecnu.edu.cn;
b Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, P. R. of China
c Graduate School of Chinese Academy of Sciences, Beijing 100039, P. R. of China
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Publication History

Received 18 January 2007
Publication Date:
08 May 2007 (online)

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Abstract

A one-pot reaction of diazoacetates, thiols and azodicarboxylates in the presence of a dirhodium acetate catalyst gave N,S-ketals in good yields. This reaction proceeded via an unusual 1,2-aza shift from a sulfonium ylide intermediate.

Key words

one-pot reaction - diazo compounds - sulfonium ylides - N,S-ketals - rearrangement reaction

    References and Notes

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10

Crystal Structure Data for 4h. C22H26N2O7S, Mw = 462.51, colorless, Triclinic, P1, a = 10.343 (2), b = 10.796 (2), c = 11.630 (2) Å, α = 106.74 (2)°, β = 102.61 (2)°, γ = 101.02 (2)°, V = 1167.93 (46) Å3, Z = 2, T = 287 (2) K, ρ calcd = 1.315 Mg·m-3, F(000) = 488, λ = 0.71073 Å, µ = 0.183 mm-1, GOF = 0.977, R(F) = 0.0435 and wR(F)2 = 0.1061 for 4930 observed reflections, I > 4σ, 1.91° < θ < 25.50°. CCDC 299823 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB21EZ, UK; fax +44 (1223)336033; or deposit@ ccdc.cam.ac.uk].