Catalytic hydrogen atom transfer from hydrosilanes to vinylarenes for hydrosilylation and polymerization
| Autor: | Kyungsuk Yum, Brad S. Pierce, Kwangho Nam, Xin Chen, Gyu Leem, Ashif Karedath, Watcharapon Prasitwatcharakorn, Jiali Gao, Parham Asgari, Yuanda Hua, Sinjinee Sardar, Chanachon Thiamsiri, Apparao Bokka, Junha Jeon |
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| Rok vydání: | 2019 |
| Předmět: |
010405 organic chemistry
Chemistry Hydrosilylation Process Chemistry and Technology Bioengineering Hydrogen atom 010402 general chemistry 01 natural sciences Biochemistry Combinatorial chemistry Catalysis Article 0104 chemical sciences 3. Good health chemistry.chemical_compound Polymerization Physics::Atomic Physics |
| Zdroj: | Nature catalysis |
| ISSN: | 2520-1158 |
| Popis: | 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 (LBCI-HAT). The catalytic LBCI-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, 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. EPR study identified a potassiated paramagnetic species and multistate density function theory revealed a high HAT character, yet multiconfigurational nature in the transition state of the reaction. Graphical Abstract |
| Databáze: | OpenAIRE |
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