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Rhodium‐Catalyzed Asymmetric [2+2+2] Cycloaddition of 1,6‐Enynes with Racemic Secondary Allylic Alcohols through Kinetic Resolution
Author(s) -
Suzuki Shunsuke,
Shibata Yu,
Tanaka Ken
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202000010
Subject(s) - kinetic resolution , allylic rearrangement , stereocenter , cycloaddition , chemistry , enyne , rhodium , diastereomer , enantiomer , cationic polymerization , stereochemistry , enantioselective synthesis , bicyclic molecule , catalysis , medicinal chemistry , organic chemistry
It has been established that a cationic rhodium(I)/P‐phos complex catalyzes the asymmetric [2+2+2] cycloaddition of 1,6‐enynes with racemic secondary allylic alcohols to produce the corresponding chiral bicyclic cyclohexenes, possessing three stereogenic centers, as a single diastereomer with excellent ee values. Mechanistic experiments revealed that the present cycloaddition proceeds through the kinetic resolution of the racemic secondary allylic alcohols, in which one enantiomer preferentially reacts with the 1,6‐enyne.