可见光/路易斯碱协同催化的三氟甲基取代烯烃脱氟硅化反应研究

doi:10.6023/cjoc202304034

摘要/Abstract

以三氟甲基取代烯烃为底物, 使用硅硼烷为硅自由基供体, 开发了一项可见光/路易斯碱协同催化的脱氟硅化反应新技术, 实现了多样性偕二氟烯丙基硅砌块的绿色高效合成. 新反应以奎宁环为路易斯碱催化剂, 通过其对硅硼键的辅助活化促进硅自由基生成, 表现出绿色温和、体系简单、易于放大、底物适用范围广和官能团兼容性强等优势. 此外, 本研究还初步展示了该类合成砌块在多类型含偕二氟甲基结构单元构建中的应用.

关键词: 可见光催化, 路易斯碱催化, 硅硼烷, 三氟甲基取代烯烃, 偕二氟烯丙基硅合成

A novel photoredox/Lewis base dual-catalytic defluorinative silylation reaction of trifluoromethylsubstituted alkenes for the synthesis of gem-difluoroallylsilanes is reported, where silylboranes are employed as the silyl donor reagents. The protocol proceeds via the catalytic activation of Si—B bond by a Lewis base quinuclidine and the formation of silyl radical, making it easy to scale up. It features mild and green reaction conditions, simple reaction system, broad substrate scope and good functional group compatibility. Furthermore, the potential of this class of building blocks in the construction of various gem-difluoromethyl-containing structures has been also demostrated.

Key words: visible light catalysis, Lewis base catalysis, silylboranes, trifluoromethyl-substituted alkenes, synthesis of gem- difluoroallylsilanes

引用此文

朱佳洁, 万义, 袁启洋, 魏金莲, 张永强. 可见光/路易斯碱协同催化的三氟甲基取代烯烃脱氟硅化反应研究[J]. 有机化学, 2023, 43(10): 3623-3634.

Jiajie Zhu, Yi Wan, Qiyang Yuan, Jinlian Wei, Yongqiang Zhang. Research of Visible Light/Lewis Base Dual Catalytic Defluorinative Silylation of Trifluoromethyl-Substituted Alkenes[J]. Chinese Journal of Organic Chemistry, 2023, 43(10): 3623-3634.

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图/表 7

图1. 代表性含偕二氟甲基的生物活性分子

Figure 1. Selected bioactive agents that contain gem-difluoro- methyl structure

图式1. 偕二氟烯丙基硅的亲核性转化和三氟甲基取代烯烃的脱氟硅化反应

Scheme 1. Nucleophilic transformations of gem-difluoroallyl- silanes and defluorinative silylation of trifluoromethyl-substituted alkenes

Entry	Photocat.	Lewis base cat.	Yield^b/% of 3a	3a/3a' ^c
1	P1	Quinuclidine	60^d	10∶1
2	P1	Quinuclidine	90	>50∶1
3	P1	DMAP	80	>50∶1
4	P1	Triphenylphosphine	54	>50∶1
5	P1	Quinuclidine	66^e	>50∶1
6	P1	—	11	—
7	P2	Quinuclidine	34	20∶1
8	P3	Quinuclidine	N.d.^f^,^g	—
9	P4	Quinuclidine	86	>50∶1
10	P5	Quinuclidine	86^g	>50∶1
11	—	Quinuclidine	Trace	—
12	P1	Quinuclidine	Trace^h	—
13	P1	Quinuclidine	53ⁱ	>50∶1
14	P1	Quinuclidine	Trace^j	—

表1. 反应条件优化a

Table 1. Optimization of reaction conditions

表2. 底物的适用性研究a

Table 2. Scope of the reaction

图式2. 反应拓展

Scheme 2. Synthetic applications

图2. 机理研究实验

Figure 2. Investigation of reaction mechanism

图式3. 建议的反应机理

Scheme 3. Proposed reaction mechanism

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