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Stereoselective Free-Radical Cycloaddition-Macrocyclization in Facile Synthesis of Trans-Cyclohexano-Fused 12-Membered Crown Thioethers

Troyansky, Emmanuil I. and Ismagilov, Rustem F. and Samoshin, Vyacheslav V. and Strelenko, Yury A. and Demchuk, Dmitry V. and Nikishin, Gennady I. and Lindeman, Sergey V. and Khrustalyov, Viktor N. and Struchkov, Yury T. (1995) Stereoselective Free-Radical Cycloaddition-Macrocyclization in Facile Synthesis of Trans-Cyclohexano-Fused 12-Membered Crown Thioethers. Tetrahedron, 51 (42). pp. 11431-11444. ISSN 0040-4020. doi:10.1016/0040-4020(95)00707-F.

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Homolytic cycloaddition of dithiols 1,2 derived from trans- and eis-1,2-cyclohexanediols to alkynes, induced by Pr3B-O2, offers an extremely simple approach to trans- and cis-cyclohexano-fused 12-membered crown thialactones 4a-c-7a-c. The reaction of trans-1 proceeds with pronounced remote 1,6-asymmetric induction to give predominantly (IS *, 6R *, 12S *)-4a–c, while cis-2 reacts nonstereoselectively. Basing on molecular mechanics calculations the stereoselectivity is rationalized as a result of entropy favored pathway of macrocyclization.

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Ismagilov, Rustem F.0000-0002-3680-4399
Additional Information:Copyright © 1995 Published by Elsevier. (Received in UK 27 June 1995; revsed 25 August 1995; accepted 1 September 1995) We are grateful to Mr R Fleming (The University of Nottingham, U.K ) for recording several NMR (400 MHz) spectra We thank the InternatIonal Science Foundation (Soros Foundation) (Grant MPL 000) and Russian Foundation of Fundamental Studies (Projects 93-03-18110 and 94-03-09296) for generous financial support E.I.T. also indebtedly thanks the Royal Society for the Kapitza Fellowship and Professor Gerald Pattenden for very helpful discussion on macrocyclization. Dedicated to Professor Nikolay S. Zefirnv on the occasion of his 60th birthday.
Funding AgencyGrant Number
International Science FoundationMPL000
Russian Foundation for Fundamental Studies93-03-18110
Russian Foundation for Fundamental Studies94-03-09296
Subject Keywords:ring-system; stereochemistry; cyclization; alkynes; construction; conformation; strategy; ethers; route
Issue or Number:42
Record Number:CaltechAUTHORS:20130821-160734712
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:40886
Deposited By: Whitney Barlow
Deposited On:29 Aug 2013 21:39
Last Modified:10 Nov 2021 04:23

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