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Enantioselective Cross‐Exchange between C−I and C−C σ Bonds
Author(s) -
Sun YuLi,
Wang XingBen,
Sun FengNa,
Chen QianQian,
Cao Jian,
Xu Zheng,
Xu LiWen
Publication year - 2019
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.201902029
Subject(s) - stereocenter , chemistry , reductive elimination , iodide , aryl , enantioselective synthesis , intramolecular force , phosphoramidite , bond cleavage , alkyl , oxidative addition , medicinal chemistry , catalysis , palladium , stereochemistry , organic chemistry , dna , biochemistry , oligonucleotide
A palladium‐catalyzed enantioselective intramolecular σ‐bond cross‐exchange between C−I and C−C bonds is realized, providing chiral indanones bearing an alkyl iodide group and an all‐carbon quaternary stereocenter. Pd/TADDOL‐derived phosphoramidite is found to be an efficient catalytic system for both C−C bond cleavage and alkyl iodide reductive elimination. In addition to aryl iodides, aryl bromides can also be used for this transformation in the presence of KI. Density‐functional theory (DFT) calculation studies support the ring‐opening of cyclobutanones occuring through an oxidative addition/reductive elimination process involving Pd IV species.