Application of Triborylmethane Reagent in the Stereoselective Synthesis of Dissymmetric gem-Diborylalkenes

doi:10.6023/cjoc202406008

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (1): 212-219.DOI: 10.6023/cjoc202406008 Previous Articles Next Articles

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次甲基三硼试剂在非对称烯基偕二硼立体选择性合成中的应用研究

杨甜甜^a^,^b, 陈都^a^,^b, 张鹏^a^,^*(), 刘超^a^,^*()

a 中国科学院兰州化学物理研究所羰基合成与选择性氧化国家重点实验室兰州 730000
b 中国科学院大学北京 100049

收稿日期:2024-06-07 修回日期:2024-08-11 发布日期:2024-09-26

Application of Triborylmethane Reagent in the Stereoselective Synthesis of Dissymmetric gem-Diborylalkenes

Tiantian Yang^a^,^b, Du Chen^a^,^b, Peng Zhang^a(), Chao Liu^a()

a State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000
b University of Chinese Academy of Sciences, Beijing 100049

Received:2024-06-07 Revised:2024-08-11 Published:2024-09-26
Contact: *E-mail: pengzhang@licp.cas.cn; chao.liu@nju.edu.cn

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Abstract

A novel triborylmethane reagent was successfully synthesized, which reacted with aldehydes under the condition of pentamethyldiethylenetriamine (PMDETA) as additive, enabling the synthesis of dissymmetrical gem-diborylalkenes. The method exhibits excellent stereoselectivity and good yields. The reaction has good substrate compatibility and the two boryl moieties in the product have different reactivities. Through cross-coupling with aryl halides, the Bpin moiety can be converted into an aryl group, achieving the stereoselective synthesis of trisubstituted vinylboronates.

Key words: gem-diborylalkenes, B—O elimination, boron reagent, aldehydes

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Tiantian Yang, Du Chen, Peng Zhang, Chao Liu. Application of Triborylmethane Reagent in the Stereoselective Synthesis of Dissymmetric gem-Diborylalkenes[J]. Chinese Journal of Organic Chemistry, 2025, 45(1): 212-219.

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Fig. & Tab. 5

Scheme 1. Strategies for the synthesis of gem-diborylalkenes

Table 1. Substrate scope of gem-diborylalkenes

Scheme 2. Plausible mechanism for stereoselectivity

Scheme 3. Gram scale synthesis of gem-diborylalkene 2a

Scheme 4. Cross coupling reaction of gem-diborylalkenes pro- duct 2a

References 14

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次甲基三硼试剂在非对称烯基偕二硼立体选择性合成中的应用研究

Application of Triborylmethane Reagent in the Stereoselective Synthesis of Dissymmetric gem-Diborylalkenes

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Fig. & Tab. 5

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