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Rhodium(I)‐Catalyzed Enantioselective Cyclization of Enynes by Intramolecular Cleavage of the Rh−C Bond by a Tethered Hydroxy Group
Author(s) -
Oonishi Yoshihiro,
Masusaki Shuichi,
Sakamoto Shunki,
Sato Yoshihiro
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201902832
Subject(s) - enantioselective synthesis , rhodium , chemistry , intramolecular force , moiety , bond cleavage , cycloaddition , stereochemistry , metathesis , catalysis , medicinal chemistry , organic chemistry , polymerization , polymer
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 ee s. 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 σ‐bond metathesis of a tethered O−H bond in the substrate. Furthermore, it was found that the cyclic compounds were obtained with high ee s even when the starting materials having a racemic secondary alcohol moiety were used in this reaction.