Iron‐Catalyzed Allylic C(sp3)−H Silylation: Spin‐Crossover‐Efficiency‐Determined Chemoselectivity

The nuanced role of spin effects remains a critical gap in designing proficient open‐shell catalysts. This study elucidates an iron‐catalyzed allylic C(sp3)−H silylation/alkyne hydrosilylation reaction, in which the spin state of the open‐shell iron catalyst dictates the reaction kinetics and pathwa...

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Published in:Angewandte Chemie International Edition Vol. 63; no. 21; pp. e202402044 - n/a
Main Authors: He, Peng, Guan, Mu‐Han, Hu, Meng‐Yang, Zhou, Yuan‐Jun, Huang, Ming‐Yao, Zhu, Shou‐Fei
Format: Journal Article
Language:English
Published: Germany Wiley Subscription Services, Inc 21.05.2024
Edition:International ed. in English
Subjects:
Alkenes
Alkynes
Catalysts
C−H bond silylation
Hydrosilylation
Iron
iron catalysis
Reaction kinetics
spin
spin crossover
spin effects
Substrates
iron catalysis
spin crossover
spin effects
spin
C−H bond silylation
ISSN:1433-7851, 1521-3773, 1521-3773
Online Access:Get full text
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Summary:The nuanced role of spin effects remains a critical gap in designing proficient open‐shell catalysts. This study elucidates an iron‐catalyzed allylic C(sp3)−H silylation/alkyne hydrosilylation reaction, in which the spin state of the open‐shell iron catalyst dictates the reaction kinetics and pathway. Specifically, spin crossover led to alkyne hydrosilylation, whereas spin conservation resulted in a novel allylic C(sp3)−H silylation reaction. This chemoselectivity, governed by the spin‐crossover efficiency, reveals an unexpected dimension in spin effects and a first in the realm of transition‐metal‐catalyzed in situ silylation of allylic C(sp3)−H bonds, which had been previously inhibited by the heightened reactivity of alkenes in hydrosilylation reactions. Furthermore, this spin crossover can either accelerate or hinder the reaction at different stages within a single catalytic reaction, a phenomenon scarcely documented. Moreover, we identify a substrate‐assisted C−H activation mechanism, a departure from known ligand‐assisted processes, offering a fresh perspective on C−H activation strategies. An iron‐catalyzed allylic C(sp3)−H silylation/alkyne hydrosilylation reaction was developed in which the spin state of the open‐shell iron catalyst dictates the reaction kinetics and pathway. This chemoselectivity, governed by the spin‐crossover efficiency, indicates an unexpected dimension in spin effects.
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ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.202402044