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Catalytic Enantioselective Cloke–Wilson Rearrangement
Author(s) -
Ortega Alesandere,
Manzano Rubén,
Uria Uxue,
Carrillo Luisa,
Reyes Efraim,
Tejero Tomas,
Merino Pedro,
Vicario Jose L.
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201804614
Subject(s) - enantioselective synthesis , catalysis , phosphoric acid , cyclopropane , brønsted–lowry acid–base theory , ring (chemistry) , chemistry , substrate (aquarium) , cope rearrangement , carroll rearrangement , stereochemistry , organic chemistry , sigmatropic reaction , oceanography , geology
Racemic cyclopropyl ketones undergo enantioselective rearrangement to deliver the corresponding dihydrofurans in the presence of a chiral phosphoric acid as the catalyst. The reaction involves activation of the donor‐acceptor cyclopropane substrate by the chiral Brønsted acid catalyst to promote the ring‐opening event, thus generating a carbocationic intermediate that subsequently undergoes cyclization. Computational studies and control experiments support this mechanistic pathway.