Si-B Functional Group Exchange Reaction Enabled by a Catalytic Amount of BH3: Scope, Mechanism, and Application | |
Department | 羰基合成与选择氧化国家重点实验室(OSSO) |
Zhang J(张炯)1,3; Wei R(魏睿)2; Ren CP(任春平)1; Liu L(刘柳)2; Wu LP(吴立朋)1 | |
The second department | 吴立朋人才团队 |
2023-07-06 | |
Source Publication | J. Am. Chem. Soc |
Volume | 145Issue:28Pages:15619-15629 |
Abstract | Functional group exchanges based on single-bond transformation are rare and challenging. In this regard, functional group exchange reactions of hydrosilanes proved to be more problematic. This is because this exchange requires the cleavage of the C–Si bond, while the Si–H bond is relatively easily activated for hydrosilanes. Herein, we report the first Si–B functional group exchange reactions of hydrosilanes with hydroboranes simply enabled by BH3 as a catalyst. Our methodology works for various aryl and alkyl hydrosilanes and different hydroboranes with the tolerance of general functional groups (up to 115 examples). Control experiments and density functional theory (DFT) studies reveal a distinct reaction pathway that involves consecutive C–Si/B–H and C–B/B–H σ-bond metathesis. Further investigations of using more readily available chlorosilanes, siloxane, fluorosilane, and silylborane for Si–B functional group exchanges, Ge–B functional group exchanges, and depolymerizative Si–B exchanges of polysilanes are also demonstrated. Moreover, the regeneration of MeSiH3 from polymethylhydrosiloxane (PMHS) is achieved. Notably, the formal hydrosilylation of a wide range of alkenes with SiH4 and MeSiH3 to selectively produce (chiral)trihydrosilanes and (methyl)dihydrosilanes is realized using inexpensive and readily available PhSiH3 and PhSiH2Me as gaseous SiH4 and MeSiH3 surrogates. |
Keyword | 催化 官能团交换 硼烷 硅烷 |
MOST Discipline Catalogue | 理学::化学 |
DOI | 10.1021/jacs.3c05625 |
URL | 查看原文 |
Indexed By | SCI |
If | 15.0 |
Language | 英语 |
compositor | 第一作者单位 |
Citation statistics | |
Document Type | 期刊论文 |
Identifier | http://ir.licp.cn/handle/362003/30576 |
Collection | 羰基合成与选择氧化国家重点实验室(OSSO) |
Corresponding Author | Zhang J(张炯); Liu L(刘柳) |
Affiliation | 1.中国科学院兰州化学物理研究所 2.南方科技大学 3.中国科学院大学 |
Corresponding Author Affilication | Lanzhou Institute of Chemical Physics,Chinese Academy of Sciences |
Recommended Citation GB/T 7714 | Zhang J,Wei R,Ren CP,et al. Si-B Functional Group Exchange Reaction Enabled by a Catalytic Amount of BH3: Scope, Mechanism, and Application[J]. J. Am. Chem. Soc,2023,145(28):15619-15629. |
APA | Zhang J,Wei R,Ren CP,Liu L,&Wu LP.(2023).Si-B Functional Group Exchange Reaction Enabled by a Catalytic Amount of BH3: Scope, Mechanism, and Application.J. Am. Chem. Soc,145(28),15619-15629. |
MLA | Zhang J,et al."Si-B Functional Group Exchange Reaction Enabled by a Catalytic Amount of BH3: Scope, Mechanism, and Application".J. Am. Chem. Soc 145.28(2023):15619-15629. |
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