Rhodium(I)-Catalyzed Decarbonylative Spirocyclization through CC Bond Cleavage of Benzocyclobutenones: An Efficient Approach to Functionalized Spirocycles

The rhodium‐catalyzed formation of all‐carbon spirocenters involves a decarbonylative coupling of trisubstituted cyclic olefins and benzocyclobutenones through CC activation. The metal–ligand combination [{Rh(CO)2Cl}2]/P(C6F5)3 catalyzed this transformation most efficiently. A range of diverse spir...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2014-02, Vol.53 (7), p.1891-1895
Main Authors: Xu, Tao, Savage, Nikolas A., Dong, Guangbin
Format: Article
Language:English
Subjects:
Activation
Bonding
Catalysis
Cleavage
Cyclization
CC activation
decarbonylation
Formations
homogeneous catalysis
Joining
Molecular Structure
Olefins
Pathways
Polycyclic Compounds - chemistry
rhodium
Rhodium - chemistry
Spiro Compounds - chemical synthesis
Spiro Compounds - chemistry
spirocycles
Stereoisomerism
Transformations
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Summary:The rhodium‐catalyzed formation of all‐carbon spirocenters involves a decarbonylative coupling of trisubstituted cyclic olefins and benzocyclobutenones through CC activation. The metal–ligand combination [{Rh(CO)2Cl}2]/P(C6F5)3 catalyzed this transformation most efficiently. A range of diverse spirocycles were synthesized in good to excellent yields and many sensitive functional groups were tolerated. A mechanistic study supports a hydrogen‐transfer process that occurs through a β‐H elimination/decarbonylation pathway. All‐carbon spirocenters were formed by a decarbonylative coupling of trisubstituted cyclic olefins and benzocyclobutenones through CC activation. The metal–ligand combination of [{Rh(CO)2Cl}2] and P(C6F5)3 catalyzed this transformation most efficiently; a range of spirocyclic rings was thus synthesized in good to excellent yields.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201310149