Journal
NATURE CATALYSIS
Volume 2, Issue 2, Pages 164-173Publisher
NATURE PUBLISHING GROUP
DOI: 10.1038/s41929-018-0217-z
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Funding
- National Institutes of Health (NIGMS) [GM116031, GM117511-01]
- ACS Petroleum Research Fund (PRF) [54831-DNI1]
- National Science Foundation (CHE) [1709369]
- Swedish Research Council [VR 2015-04114]
- University of Texas at Arlington
- NSF [CHE-0234811, CHE-0840509]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1709369] Funding Source: National Science Foundation
- Swedish Research Council [2015-04114] Funding Source: Swedish Research Council
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Because of the importance of hydrogen atom transfer (HAT) in biology and chemistry, there is increased interest in new strategies to perform HAT in a sustainable manner. Here, we describe a sustainable, net redox-neutral HAT process involving hydrosilanes and alkali metal Lewis base catalysts-eliminating the use of transition metal catalysts-and report an associated mechanism concerning Lewis base-catalysed, complexation-induced HAT. The catalytic Lewis base-catalysed, complexation-induced HAT is capable of accessing both branch-specific hydrosilylation and polymerization of vinylarenes in a highly selective fashion, depending on the Lewis base catalyst used. In this process, the Earth-abundant, alkali metal Lewis base catalyst plays a dual role. It first serves as a HAT initiator and subsequently functions as a silyl radical stabilizing group, which is critical to highly selective cross-radical coupling. An electron paramagnetic resonance study identified a potassiated paramagnetic species, and multistate density functional theory revealed a high HAT character, yet multiconfigurational nature in the transition state of the reaction.
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