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Palladium‐Mediated Dynamic Kinetic Resolution: Stereoselective Synthesis of Vicinal Diamines
Author(s) -
Cook Gregory R.,
Shanker P. Sathya,
Pararajasingham Ketheeswaran
Publication year - 1999
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/(sici)1521-3773(19990115)38:1/2<110::aid-anie110>3.0.co;2-l
Subject(s) - palladium , stereocenter , chemistry , kinetic resolution , diastereomer , allylic rearrangement , vicinal , stereoselectivity , nucleophile , selectivity , nucleophilic substitution , substitution reaction , stereochemistry , catalysis , enantioselective synthesis , organic chemistry
Can an adjacent stereocenter control selectivity in the palladium‐catalyzed allylic substitution reaction? If the intermediate π‐allyl palladium complex can undergo rapid inversion, the answer is yes (see reaction scheme). Starting from chiral 5‐vinyloxazolidinones, trapping of intermediates 1 and 2 , which are in a dynamic equilibrium, with nitrogen‐containing nucleophiles leads to the quantitative formation of diamines as single diastereomers.