open access

https://hdl.handle.net/2115/78679

Rhodium(I)-Catalyzed Enantioselective Cyclization of Enynes by Intramolecular Cleavage of the Rh-C Bond by a Tethered Hydroxy Group

英語

sigma-bond metathesis

2019-06-24

Wiley-Blackwell

Angewandte chemie-international edition

58(26)

8736-8739

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(sp(2)) bond in the rhodacyclopentene intermediate, which was formed by enantioselective oxidative cycloaddition of enynes to a chiral rhodium(I) complex, was intramolecularly cleaved by sigma-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.

学術雑誌論文

Accepted Manuscript

This is the peer reviewed version of the following article: Angewandte chemie-international edition,58(26),8736-8739,(2019), which has been published in final form at https://doi.org/10.1002/anie.201902832 . This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.

1433-7851