三苯基砷/铱催化的非活化一级碳氢键的双硼化反应合成1,1-偕二硼烷

doi:10.6023/cjoc202111032

摘要/Abstract

报道了以吡唑作为导向基, 三苯基砷/铱催化的活化一级碳氢键的双硼化反应. 这一方法能够兼容多种官能团, 能够以中等到良好的收率实现一系列1,1-偕二硼烷类化合物的合成. 同时, 这一方法也能够实现克级规模的反应, 所获得的硼化产物能够实现进一步的转化.

关键词: 碳氢键活化, 有机硼, 合成方法, 铱

The AsPh₃/iridium catalyzed diborylation of unactivated primary C(sp³)—H bonds using pyrazoles as directing groups was disclosed. This method could tolerate a variety of functional groups, affording a vast array of 1,1-diboron alkanes in moderate to good yields. The synthetic utility of the current method on a gram-scale reaction for further functionalization was also demonstrated.

Key words: C—H borylation, organoboron, synthetic methods, iridium

引用此文

刘文启, 沈振陆, 徐森苗. 三苯基砷/铱催化的非活化一级碳氢键的双硼化反应合成1,1-偕二硼烷[J]. 有机化学, 2022, 42(4): 1101-1110.

Wenqi Liu, Zhenlu Shen, Senmiao Xu. Synthesis of 1,1-Diboron Alkanes via Diborylation of Unactivated Primary C(sp³)—H Bonds Enabled by AsPh₃/Iridium Catalysis[J]. Chinese Journal of Organic Chemistry, 2022, 42(4): 1101-1110.

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参考文献 27

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Entry	Ligand	Solvent	Yield^b/%
1	None	n-Hexane	63
2	P(C₆F₅)₃	n-Hexane	51
3	P(4-CF₃-C₆H₄)₃	n-Hexane	51
4	AsPh₃	n-Hexane	79
5^c	AsPh₃	n-Hexane	Trace
6^d	AsPh₃	n-Hexane	59
7^e	AsPh₃	n-Hexane	57
8^f	AsPh₃	n-Hexane	51
9	AsPh₃	Cyclohexane	82
10	AsPh₃	THF	51
11	AsPh₃	1,4-Dioxane	51

Entry	Ligand	Solvent	Yield^b/%
1	None	n-Hexane	63
2	P(C₆F₅)₃	n-Hexane	51
3	P(4-CF₃-C₆H₄)₃	n-Hexane	51
4	AsPh₃	n-Hexane	79
5^c	AsPh₃	n-Hexane	Trace
6^d	AsPh₃	n-Hexane	59
7^e	AsPh₃	n-Hexane	57
8^f	AsPh₃	n-Hexane	51
9	AsPh₃	Cyclohexane	82
10	AsPh₃	THF	51
11	AsPh₃	1,4-Dioxane	51