Visible-Light-Driven Photocatalytic Kharasch Reaction of Phenol/ Arylamine-Linked 1,6-Enynes with Perhalogenated Methane

doi:10.6023/cjoc202211011

Abstract

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

Cite this article

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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Fig. & Tab. 9

Figure 1. Some benzofurans -containing natural products

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

Table 1. Condition optimization for product 3a

Figure 2. X-ray strcutre of product 3a

Scheme 2. Substrate scope for the synthesis of products 3

Scheme 3. Application of compound 3a

Scheme 4. Control experiments of the formation of 3a

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)

Scheme 5. Proposed pathway toward product 3

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可见光驱动酚/芳胺联-1,6-烯炔与全卤代甲烷的Kharasch反应