可见光驱动酚/芳胺联-1,6-烯炔与全卤代甲烷的Kharasch反应

doi:10.6023/cjoc202211011

摘要/Abstract

1,n-烯炔合成子参与的涉及原子转移过程的自由基环化碳卤官能化是一类有效且实用的方法, 它通过利用原子转移试剂中碳卤σ键的自由基龟裂及其在烯炔母核π键上的移位来实现卤代环系结构的有序构建, 展现了完全原子经济性. 近年来, 该类反应成为研究热点之一. 报道了一类通用可见光催化的酚/芳胺联-1,6-烯炔和全卤代甲烷(如三氯溴甲烷或四溴化碳)参与的环化碳卤官能团化反应, 在温和且无氧化剂条件下原子经济且高效地合成了一系列作为主要立体异构体的(Z)-2,3-二氢苯并呋喃和(Z)-吲哚啉衍生物, 收率优良, 其中大部分产物仅以(Z)-构型被合成. 该反应具有底物范围广、官能团耐受性高、高原子经济以及高立体选择性等优点, 为2,3-二氢苯并呋喃和吲哚啉杂环的合成提供一类绿色、原子经济、高效的合成策略.

关键词: 可见光催化反应, 环化碳卤官能化反应, 原子经济性, 2,3-二氢苯并呋喃衍生物

Radical annulative carbohalofunctionalization of 1,n-enynes via atom transfer processes constitutes an efficient and practical synthetical strategy for accessing halogenated cyclic structures with complete atom economy through radical cleavage of a pre-existing carbon-halogen σ-bond of an atom transfer reagent and their transposition over the π-bond of enyne motifs. Recently, such reaction has become one of hot topics. A general photocatalytic annulative carbohalogenation of phenol/arylamine-linked 1,6-enynes with perhalogenated methanes such as BrCCl₃ or CBr₄ is disclosed, leading to the atom-economic, efficient synthesis of functionalized (Z)-2,3-dihydrobenzofurans and (Z)-indolines as main stereoisomers with good yields and high stereoselectivity under mild and oxidant-free conditions, in which only (Z)-configuration was observed in most products. This protocol demonstrates wide substrate scope, high functional group tolerance, and high atom economy as well as high stereoselectivity, providing a green, atom-economic and efficient method toward 2,3-dihydrobenzofurans and indolines.

Key words: photocatalysis, annulative carbohalogenation, atom economy, 2,3-dihydrobenzofurans

引用此文

季晓霜, 付荣, 王树良, 郝文娟, 姜波. 可见光驱动酚/芳胺联-1,6-烯炔与全卤代甲烷的Kharasch反应[J]. 有机化学, 2022, 42(12): 4282-4291.

Xiaoshuang Ji, Rong Fu, Shuliang Wang, Wenjuan Hao, Bo Jiang. Visible-Light-Driven Photocatalytic Kharasch Reaction of Phenol/ Arylamine-Linked 1,6-Enynes with Perhalogenated Methane[J]. Chinese Journal of Organic Chemistry, 2022, 42(12): 4282-4291.

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图/表 9

图1. 若干含二氢苯并呋喃骨架的天然产物及活性分子

Figure 1. Some benzofurans -containing natural products

图式1. (Z)-2,3-二氢苯并呋喃和(Z)-吲哚啉衍生物的立体选择性合成

Scheme 1. Stereoselective synthesis of (Z)-2,3-dihydrobenzo- furans and (Z)-indolines

Entry	Variation from the established conditions	Yield^b/%
1	None	92
2	NaOAc instead of K₂HPO₄	83
3	K₃PO₄ instead of K₂HPO₄	87
4	DMAP instead of K₂HPO₄	82
5	TEA instead of K₂HPO₄	75
6	DMF instead of EtOH	86
7	DCE instead of EtOH	61
8	Acetone instead of EtOH	37
9	1,4-Dioxane instead of EtOH	71
10	Ru(ppy)₂Cl instead of fac-Ir(ppy)₃	78
11	Eosin Y instead of fac-Ir(ppy)₃	73
12	4CzIPN instead of fac-Ir(ppy)₃	66
13	0.10 mol% of fac-Ir(ppy)₃	92

表1. 化合物3a反应条件的优化a

Table 1. Condition optimization for product 3a

图2. 化合物3a的单晶衍射图

Figure 2. X-ray strcutre of product 3a

图式2. 合成产物3的底物范围

Scheme 2. Substrate scope for the synthesis of products 3

图式3. 化合物3a的应用

Scheme 3. Application of compound 3a

图式4. 形成产物3a的控制实验

Scheme 4. Control experiments of the formation of 3a

图3. fac-Ir(ppy)3与1a的发光淬灭实验(a, b), 以及fac-Ir(ppy)3与2a的发光淬灭实验(c, d)

Figure 3. Luminescence quenching of fac-Ir(ppy)3 with 1a (a, b), and luminescence quenching of fac-Ir(ppy)3 with 2a (c, d)

图式5. 生成化合物3的可能机理

Scheme 5. Proposed pathway toward product 3

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