1.
Angew Chem Int Ed Engl
; 58(26): 8736-8739, 2019 Jun 24.
Article
in English
| MEDLINE
| ID: mdl-31017719
ABSTRACT
Rhodium(I)-catalyzed enantioselective intramolecular cyclization of enynes having a hydroxy group in the tether was investigated, and various cyclic compounds possessing a chiral quaternary carbon center were obtained in high yields with high ees. In this cyclization, a Rh-C(sp2 ) bond in the rhodacyclopentene intermediate, which was formed by enantioselective oxidative cycloaddition of enynes to a chiral rhodium(I) complex, was intramolecularly cleaved by σ-bond metathesis of a tethered O-H bond in the substrate. Furthermore, it was found that the cyclic compounds were obtained with high ees even when the starting materials having a racemic secondary alcohol moiety were used in this reaction.