Title

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

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.

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