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Rhodium‐Catalyzed Asymmetric Cycloisomerization and Parallel Kinetic Resolution of Racemic Oxabicycles
Author(s) -
Loh Charles C. J.,
Schmid Matthias,
Webster Robert,
Yen Andy,
Yazdi Shabnam K.,
Franke Patrick T.,
Lautens Mark
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201604937
Subject(s) - cycloisomerization , nucleophile , enantioselective synthesis , rhodium , kinetic resolution , chemistry , intramolecular force , catalysis , intermolecular force , stereochemistry , organic chemistry , molecule
While desymmetrizations by intermolecular asymmetric ring‐opening reactions of oxabicyclic alkenes with various nucleophiles have been reported over the past two decades, the demonstration of an intramolecular variant is unknown. Reported herein is the first rhodium‐catalyzed asymmetric cycloisomerization of meso ‐oxabicyclic alkenes tethered to bridgehead nucleophiles, thus providing access to tricyclic scaffolds through a myriad of enantioselective C−O, C−N, and C−C bond formations. Moreover, we also demonstrate a unique parallel kinetic resolution, whereby racemic oxabicycles bearing two different bridgehead nucleophiles can be resolved enantioselectively.