Research of the Stereoselectivity and Mechanism of the Hydroboration Reaction Between B(C6F5)3/Ammonium Chloride Systems with Terminal Alkyne

doi:10.6023/A17040141

Acta Chim. Sinica ›› 2017, Vol. 75 ›› Issue (8): 824-830.DOI: 10.6023/A17040141 Previous Articles

Article

有机胺盐/硼烷体系与炔烃的硼氢化加成反应机理研究

孙国峰, 苏敏, 方洁, Borzov Maxim, 聂万丽

乐山师范学院化学学院天然产物化学与小分子催化四川省高校重点实验室乐山 614000

投稿日期:2017-04-06 发布日期:2017-05-24
通讯作者: 聂万丽,E-mail:niewl126@126.com E-mail:niewl126@126.com
基金资助:
项目受国家自然科学基金（No.21542011）和四川省教育厅及乐山市科技局（Nos.15ZB0256，Z14GZ010）资助.

Research of the Stereoselectivity and Mechanism of the Hydroboration Reaction Between B(C₆F₅)₃/Ammonium Chloride Systems with Terminal Alkyne

Sun Guofeng, Su Min, Fang Jie, Borzov Maxim, Nie Wanli

Sichuan Province Key Laboratory of Natural Products and Small Molecule Synthesis, Chemical Department of Leshan Normal University, Leshan 614000, China

Received:2017-04-06 Published:2017-05-24
Contact: 10.6023/A17040141 E-mail:niewl126@126.com
Supported by:
Project supported by the National Natural Science Foundation of China (No.21542011),Scientific Research Fund of Sichuan Educational Department and Leshan Technology Division (Nos.15ZB0256,Z14GZ010).

1. Research of the Stereoselectivity and Mechanism of the Hydroboration Reaction Between B(C₆F₅)₃/Ammonium Chloride Systems with Terminal Alkyne.PDF(1428KB)

Abstract

Stereoselective hydroboration reaction of alkynes has been considered as one of the most important organic reaction. To date a handful of metal-catalyzed systems have been demonstrated to achieve trans-hydroboration of alkynes. This paper describes the first non-metal-catalyzed systems which could stereoselectively hydroborate the terminal alkynes in a trans-configuration. The Lewis acid B(C₆F₅)₃ and ammonium chloride have been used as the reaction substrates, and phenylsilane as the hydride source. The hydroboration reaction could be performed in a one-pot procedure by mixing of B(C₆F₅)₃, ammonium chloride and silane together in an equivalent amount. But this one-pot reaction is not so nice since there is always mixed with the ammonium hydroborate[R₂NH₂]⁺[H-B(C₆F₅)₃]^- intermediates products. A series of ammonium hydroborates prepared from the corresponding primary, secondary, tertiary and quaternary amine hydrochlorides have been isolated, and used in the directly hydroboration with terminal alkynes. To our surprise the ammonium hydroborate[R₂NH₂]⁺[H-B(C₆F₅)₃]^- could not react with the alkynes alone. When using[R₂NH₂]⁺[H-B(C₆F₅)₃]^- to react with alkynes, trace amount of catalytic Lewis acid B(C₆F₅)₃ is necessary to firstly activate the carbon-carbon triple bonds and form the crucial zwitterionic σ-complexes. The mechanism study has shown that different from the typical Lewis acid/Lewis base FLPs system reacted with alkynes, in this B(C₆F₅)₃/ammonium chloride system the ammonium chloride plays an important role on the stereoselective control of the reaction. The week interaction between the Cl ion and B(C₆F₅)₃ in the σ-complexes has not only slowed down the unfavorite 1,1-carboboration reaction, but also stabilized the σ-complexes which has offer the chance for the nucleophilic reagent to attack the reaction center in a cis-or trans-mode. In our experiment the bulky ion[H-B(C₆F₅)₃]-could only attach the active alkynes from the trans-side and form the Z-hydroboration product. This work demonstrates that the combination of the ammonium halides with the Lewis acid B(C₆F₅)₃ could act as a novel "frustrated Lewis pair" to activate alkynes, and will enable the development of even more sophisticated FLP and related catalyzed reactions.

Key words: ammonium chloride, B(C₆F₅)₃, silane, alkyne, hydroboration

Cite this article

Sun Guofeng, Su Min, Fang Jie, Borzov Maxim, Nie Wanli. Research of the Stereoselectivity and Mechanism of the Hydroboration Reaction Between B(C₆F₅)₃/Ammonium Chloride Systems with Terminal Alkyne[J]. Acta Chim. Sinica, 2017, 75(8): 824-830.

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[25] Detailed experimental procedures, characterization and X-ray data are available from the Supporting Information. (一些有代表性的氯代硼胺盐及炔烃硼氢化胺盐的合成、结构及X-射线单晶结构详见支持信息.)

有机胺盐/硼烷体系与炔烃的硼氢化加成反应机理研究

Research of the Stereoselectivity and Mechanism of the Hydroboration Reaction Between B(C₆F₅)₃/Ammonium Chloride Systems with Terminal Alkyne

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