Rhodium(II)-catalyzed aziridination of allyl-substituted sulfonamides and carbamates

The Journal of Organic Chemistry
Albert PadwaThomas Stengel

Abstract

Several unsaturated sulfonamides underwent intramolecular aziridination when treated with PhI(OAc)(2), MgO, and catalytic Rh(2)(OAc)(4) to give bicyclic aziridines in excellent yield. Treatment of the resulting azabicyclic sulfonamides in methanol in the presence of p-TsOH resulted in exclusive opening of the aziridine ring at the most substituted position affording six- and seven-membered ring products in high yield. In contrast, the intramolecular aziridination of several cycloalkenyl-substituted carbamates did not require a Rh(II) catalyst and proceeded via an iminoiodinane intermediate. The resulting tricyclic aziridines underwent ring opening when treated with various nucleophiles to give anti-derived products as expected for nucleophilic attack at the three-membered ring. The iodine(III)-mediated reaction of a 3-indolyl-substituted carbamate, however, required a Rh(II) catalyst. The expected aziridine was not observed, but rather simultaneous spirocyclization of C(3) and stereoselective syn-acylation at C(2) occurred to give compound 41, whose structure was unequivocally established by an X-ray crystallographic study. The reaction proceeds in a stepwise manner via a metal-free zwitterionic intermediate which is attacked b...Continue Reading

References

Aug 5, 1997·Chemical Reviews·Robert E. Babine, Steven L. Bender
Mar 1, 2002·Organic Letters·Elana Levites-AgababaChristian M Rojas
Sep 18, 2003·Journal of the American Chemical Society·Andrew Hinman, J Du Bois

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Citations

Sep 8, 2011·Chemical Reviews·K C Majumdar, Shovan Mondal
Sep 2, 2008·Journal of the American Chemical Society·John V Mulcahy, J Du Bois
Mar 29, 2011·Organic Letters·Luke A BoralskyJennifer M Schomaker
May 2, 2008·Organic Letters·María Jiménez-Hopkins, Paul R Hanson
Feb 8, 2007·Chemical Communications : Chem Comm·Christopher J HayesLesley A Humphries
May 8, 2010·Chemical Communications : Chem Comm·Florence ColletPhilippe Dauban
Apr 7, 2010·Chemical Communications : Chem Comm·George C FeastJeremy Robertson
Mar 25, 2011·Chemical Communications : Chem Comm·Chang-Bin YuYong-Gui Zhou
May 4, 2016·Journal of the American Chemical Society·John V MulcahyJ Du Bois
Jun 27, 2017·Journal of the American Chemical Society·Huiling JiangX Peter Zhang
Aug 3, 2016·Chemical Communications : Chem Comm·Shichao RenTeck-Peng Loh
Jan 30, 2010·Angewandte Chemie·Stéphane BeaumontPhilippe Dauban
Apr 21, 2009·Angewandte Chemie·Paul M Wehn, J Du Bois
Mar 11, 2010·Chemistry : a European Journal·Jimei MaXue-Wei Liu
May 19, 2010·Organic & Biomolecular Chemistry·Jeremy RobertsonTimothy D W Claridge
Nov 2, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·John F Berry
Jan 6, 2011·Chemistry : a European Journal·Timothy J DonohoeAkshat H Rathi
Jun 4, 2016·Chemistry : a European Journal·Jennifer CiesielskiPhilippe Dauban
Aug 24, 2017·Angewandte Chemie·Yong-Qiang ZhangAndreas Gansäuer
Mar 10, 2009·Angewandte Chemie·Toshiki KurokawaJ Du Bois
Apr 20, 2017·Organic & Biomolecular Chemistry·Hélène LebelMatthias Ernzerhof
Dec 14, 2011·Chemistry : a European Journal·Nicolas GigantPhilippe Dauban
Jun 26, 2012·Angewandte Chemie·Geoffroy DequirezPhilippe Dauban
Jun 19, 2014·Chemistry : a European Journal·Geoffroy DequirezPhilippe Dauban
Dec 3, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Alaa A HassanHendawy N Tawfeek
Sep 2, 2009·The Journal of Organic Chemistry·Shigeki SatoYoshiharu Iwabuchi
Jan 19, 2010·Organic Letters·Fei LiuSébastien Thibaudeau
Apr 23, 2021·Journal of the American Chemical Society·Euijae LeeSukbok Chang
Jul 10, 2021·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Changcheng JingJohn F Bower
Feb 7, 2012·The Journal of Organic Chemistry·Jared W RigoliJennifer M Schomaker
Oct 7, 2011·Organic Letters·Masafumi NakanishiRobert H Dodd

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