Enantioselective Cross‐Exchange between C−I and C−C σ Bonds

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 bo...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2019-05, Vol.58 (20), p.6747-6751
Main Authors: Sun, Yu‐Li, Wang, Xing‐Ben, Sun, Feng‐Na, Chen, Qian‐Qian, Cao, Jian, Xu, Zheng, Xu, Li‐Wen
Format: Article
Language:English
Subjects:
Aromatic compounds
asymmetric catalysis
Bromides
Catalysis
Covalent bonds
C−C activation
Enantiomers
Exchanging
Iodides
Palladium
reaction mechanisms
small-ring systems
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Summary: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 PdIV species. In exchange: An enantioselective cross‐exchange between C−I and C−C bonds is realized by palladium‐catalyzed sequential oxidative addition and reductive elimination. Chiral indanones bearing an alkyl iodide group and an all‐carbon quaternary stereocenter are synthesized in good yields and enantioselectivities.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201902029