Diastereoselective synthesis of polysubstituted tetrahydropyrans and thiacyclohexanes via indium trichloride mediated cyclizations

• Published in: Journal of organic chemistry 2001-02, Vol.66 (3), p.739-747
• Main Authors: Yang, X F, Mague, J T, Li, C J
• Format: Article
• Language: English
• ISSN: 0022-3263
• DOI: 10.1021/jo001136i

Polysubstituted tetrahydropyrans and thiacyclohexanes were synthesized in high yields with excellent diastereoselectivities via indium trichloride mediated cyclizations between homoallyl alcohols and mercaptans with aldehydes. In the case of tetrahydropyran products, the stereochemistry of the product was found to be directly correlated with the geometry of the homoallyl alcohols; whereas the cross-cyclization of aldehydes with trans-homoallyl alcohols generated (up-down-up) 2,3,4-trisubstituted tetrahydropyran products exclusively, the reaction of aldehydes with cis-homoallyl alcohols provided mainly (up-up-up) 2,3,4-trisubstituted products. When a trisubstituted homoallyl alcohol was used, its cross-cyclization with aldehydes generated (up-down-up-down-up) pentasubstituted tetrahydropyran derivatives with simultaneous controlling of five stereogenic centers. On the other hand, a cyclization-decyclization equilibrium was observed in the formation of thiacyclohexanes. The reaction of both cis- and trans-homoallyl mercaptans with aldehydes provided the same major diastereomers.