Stereoselective Free Radical Cycloaddition-macrocyclization in Facile Synthesis of trans-cyclohexano-fused 12-membered Crown Thioethers

Authors

Emmanuil I. Troyansky, Russian Academy of Sciences
Rustem F. Ismagilov, Russian Academy of Sciences
Vyacheslav V. Samoshin, Moscow State Academy of Fine Chemical Technology
Yury A. Strelenko, Russian Academy of Sciences
Dmitry V. Demchuk, Russian Academy of Sciences
Gennady I. Nikishin, Russian Academy of SciencesFollow
Sergey V. Lindeman, Marquette UniversityFollow
Viktor N. Khrustalyov, Russian Academy of SciencesFollow
Yury T. Struchkov, Russian Academy of SciencesFollow

Document Type

Article

Language

eng

Publication Date

10-1995

Publisher

Elsevier

Source Publication

Tetrahedron

Source ISSN

0040-4020

Abstract

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.

Comments

Tetrahedron, Vol. 51, No. 42 (October 16, 1995): 11431-11444. DOI.

Sergey V. Lindeman was affiliated with the Russian Academy of Sciences.

Recommended Citation

Troyansky, Emmanuil I.; Ismagilov, Rustem F.; Samoshin, Vyacheslav V.; Strelenko, Yury A.; Demchuk, Dmitry V.; Nikishin, Gennady I.; Lindeman, Sergey V.; Khrustalyov, Viktor N.; and Struchkov, Yury T., "Stereoselective Free Radical Cycloaddition-macrocyclization in Facile Synthesis of trans-cyclohexano-fused 12-membered Crown Thioethers" (1995). Chemistry Faculty Research and Publications. 640.
https://epublications.marquette.edu/chem_fac/640