Stereoselective synthesis of chiral sulfilimines from N-mesyloxycarbamates: metal-nitrenes versus metal-nitrenoids species

The Journal of Organic Chemistry
Hélène Lebel, Henri Piras

Abstract

The synthesis of a variety of chiral sulfilimines and sulfoximines is described. The amination of thioethers with a chiral N-mesyloxycarbamate was achieved in high yields and stereoselectivities using Rh2[(S)-nttl]4 as catalyst in the presence of 4-dimethylaminopyridine (DMAP) and a pyridinium salt, such as bis(DMAP)CH2Cl2 or a viologen salt. These additives proved instrumental to enhance both the yield and the stereochemical discrimination of the reaction. Mechanistic studies and control experiments have elucidated the role of these additives. DMAP served as an apical ligand for the rhodium catalyst: an X-ray crystal structure of the (DMAP)2·[Rh2{(S)-nttl}4] complex was obtained. This complex displayed a lower and irreversible redox potential. Control experiments with preformed Rh(II)-Rh(III) complex suggested such a catalytically active species in the thioether amination process. Diastereoselectivities were influenced by the sulfonyloxy leaving group, ruling out the possibility of a common metal nitrene species and instead suggesting a rhodium-nitrenoid complex. It is believed that the bispyridinium salt played the role of a phase transfer catalyst, influencing both the yield and the diastereoselectivity of the reaction.

References

Jun 30, 2001·The Journal of Organic Chemistry·A L Marzinzik, K B Sharpless
Apr 26, 2003·Organic Letters·Huw M L Davies, Chandrasekar Venkataramani
Sep 18, 2004·The Journal of Organic Chemistry·Alberto CrediAndrea Secchi
Oct 21, 2004·Journal of the American Chemical Society·Arthur J CatinoMichael P Doyle
Oct 13, 2005·Journal of the American Chemical Society·Hélène LebelSylvain Lectard
Oct 21, 2005·Organic Letters·Gae Young Cho, Carsten Bolm
May 19, 2006·Organic Letters·Olga García Mancheño, Carsten Bolm
May 31, 2007·Chemistry : a European Journal·Olga García Mancheño, Carsten Bolm
Oct 20, 2007·Organic Letters·Hélène LebelMichaël Parmentier
Oct 20, 2007·Chemical Reviews·Mohamed MellahEmmanuelle Schulz
Jan 12, 2008·Angewandte Chemie·Yuanhua WangMichael P Doyle
Jun 3, 2008·Chemistry : a European Journal·Kim Huard, Hélène Lebel
Jun 28, 2008·Journal of the American Chemical Society·David N Zalatan, J Du Bois
Aug 14, 2008·Chemistry : a European Journal·Benoît GadenneAlberto Credi
Aug 30, 2008·The Journal of Organic Chemistry·Hiroyuki MoritaTakeshi Akasaka
Nov 7, 2008·Organic Letters·Florence ColletPhilippe Dauban
Mar 4, 2009·Organic Letters·Alan Armstrong, Daniel P G Emmerson
Apr 16, 2009·The Journal of Physical Chemistry. B·Ester MarottaGiacomo Saielli
May 16, 2009·Journal of the American Chemical Society·David N Zalatan, J Du Bois
May 28, 2009·Journal of the American Chemical Society·Andrew DeAngelisJoseph M Fox
May 29, 2009·Organic Letters·Olga García MancheñoCarsten Bolm
Sep 5, 2009·Science·Roberto VanacoreBilly G Hudson
Jan 29, 2010·Chemical Communications : Chem Comm·David MarcouxAndré B Charette
May 12, 2010·Chemical Communications : Chem Comm·Andrew DeAngelisJoseph M Fox
May 18, 2010·The Journal of Organic Chemistry·Alexander B RudineCarl C Wamser
Jun 10, 2010·Journal of the American Chemical Society·Michael A IschayTehshik P Yoon
Jun 24, 2010·Chemistry : a European Journal·Masahito OchiaiWaro Nakanishi
Jan 8, 2011·Nature Protocols·Xavier Bantreil, Steven P Nolan
Apr 21, 2011·Chemistry : a European Journal·Katherine P Kornecki, John F Berry
May 20, 2011·Journal of the American Chemical Society·Xiaochen WangMichael P Doyle

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Citations

Dec 9, 2015·The Journal of Organic Chemistry·Lili ZhaoYuanhua Wang
Aug 14, 2020·Organic & Biomolecular Chemistry·Tao FengJunming Mo
Apr 20, 2017·Organic & Biomolecular Chemistry·Hélène LebelMatthias Ernzerhof
Apr 30, 2020·Chemical Reviews·Elżbieta Wojaczyńska, Jacek Wojaczyński
May 21, 2015·The Journal of Organic Chemistry·Marina ZenzolaJames A Bull
Aug 10, 2019·Journal of the American Chemical Society·Ze-Xin ZhangMichael C Willis

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