Theoretical insight into the mechanism, regioselectivity, and substituent group effect of Rh-catalyzed synthesis of 1,2-benzothiazines from NH-sulfoximines and diazo compounds

Organic & Biomolecular Chemistry
Jing YanDongju Zhang

Abstract

This work presents a computational study of RhIII-catalyzed synthesis of 1,2-benzothiazines from NH-sulfoximines and diazo compounds reported by Bolm et al. (Angew. Chem., Int. Ed., 2015, 54, 12349). The reaction involves five sequent processes: elimination of dinitrogen, C-H activation, carbene insertion, protonation, and dehydration, and the C-H activation is identified as the rate-determining step with a barrier of 33.1 kcal mol-1. Phenyl sulfoximine is found to be the most favorable substrate with the lowest barrier in comparison with methoxybenzene sulfoximine and nitrobenzene sulfoximine. The noncovalent interaction is indicated to be mainly responsible for the experimentally observed regioselectivity. The theoretical results are expected to provide valuable guidance and assistance for the synthesis of 1,2-benzothiazines.

References

Sep 15, 1988·Physical Review A: General Physics·A D Becke
Aug 24, 1999·Angewandte Chemie·M Harmata, N Pavri
Oct 5, 2001·Journal of Medicinal Chemistry·G J WellsR Bihovsky
May 8, 2003·Journal of the American Chemical Society·Michael Harmata, Xuechuan Hong
Mar 12, 2004·Bioorganic & Medicinal Chemistry Letters·Ron BihovskyGregory J Wells
Apr 22, 2006·The Journal of Organic Chemistry·Michael HarmataCharles L Barnes
Feb 24, 2011·Journal of the American Chemical Society·Xia ZhaoJianbo Wang
Dec 14, 2011·Journal of Computational Chemistry·Tian Lu, Feiwu Chen
Aug 7, 2012·Journal of the American Chemical Society·Wai-Wing ChanWing-Yiu Yu
Aug 13, 2013·Angewandte Chemie·Ulrich Lücking
Aug 26, 2014·Pesticide Biochemistry and Physiology·Thomas C SparksJames D Thomas
Nov 2, 2014·Chemistry : a European Journal·Wen AiBing Zhou
May 6, 2015·Chemical Society Reviews·Vincent BizetCarsten Bolm
Feb 1, 2008·Journal of Chemical Theory and Computation·Julian Tirado-Rives, William L Jorgensen
Nov 9, 2016·European Journal of Medicinal Chemistry·Marcus FringsChristian Gnamm
Dec 2, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Lingli HanTao Liu

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