Nickel‐Catalyzed Switchable Site‐Selective Alkene Hydroalkylation by Temperature Regulation

Regiodivergent alkene functionalization that produces either regioisomer starting from the same raw materials is desirable. Herein, we report a nickel‐catalyzed switchable site‐selective alkene hydroalkylation. The selection of reaction temperatures leads to protocols that provide regiodivergent hyd...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2022-08, Vol.61 (31), p.e202205537-n/a
Main Authors: Wang, Jia‐Wang, Liu, De‐Guang, Chang, Zhe, Li, Zhen, Fu, Yao, Lu, Xi
Format: Article
Language:English
Subjects:
Alkylamines
Amines
Asymmetric Catalysis
Chain-Walking
Cross-Coupling
Hydroalkylation
Intermediates
Nickel
Raw materials
Selectivity
Substrates
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Summary:Regiodivergent alkene functionalization that produces either regioisomer starting from the same raw materials is desirable. Herein, we report a nickel‐catalyzed switchable site‐selective alkene hydroalkylation. The selection of reaction temperatures leads to protocols that provide regiodivergent hydroalkylated products starting from a single alkene substrate. This protocol allows the convenient synthesis of α‐ and β‐branched protected amines, both of which are important to the fields of pharmaceutical chemistry and biochemistry. In addition, enantioenriched β‐branched alkylamines can be accessed in a catalytic asymmetric variant. Preliminary mechanistic studies indicate that the formation of a more stable nickelacycle provides the driving force of migration. The thermodynamic and kinetic properties of different reduction elimination intermediates are responsible for the switchable site‐selectivity. A nickel‐catalyzed switchable site‐selective alkene hydroalkylation was developed. The selection of reaction temperatures led to protocols that provide regiodivergent hydroalkylated products starting from a single alkene substrate.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202205537