Photoinduced Ru-Catalyzed meta-Selective C—H Alkylation of Phenol Derivatives

doi:10.6023/cjoc202604017

Abstract

A photo-induced ruthenium-catalyzed meta-alkylation of phenol derivatives is reported. Compared with conventional thermal reactions, it features mild conditions and good functional group tolerance, thus allowing efficient late-stage functionalization. Mechanistic studies reveal a single-electron transfer (SET) pathway involving a photo-excited ruthenacycle intermediate.

Key words: meta-selectivity, photoredox catalysis, ruthenium catalysis, late-stage functionalization

Cite this article

Xueying Cao, Chenwei Liang, Yaohang Cheng, Guanghui An. Photoinduced Ru-Catalyzed meta-Selective C—H Alkylation of Phenol Derivatives[J]. Chinese Journal of Organic Chemistry, 2026, 46(10): 4129-4040.

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Fig. & Tab. 7

Scheme 1. meta-C—H functionalization strategies

Entry	Deviation from the standard conditions	Yield^b/%	Entry	Deviation from the standard conditions	Yield^b/%
1	None	78	7	KHCO₃ instead of KOAc	62
2^c	None	56	8	K₂CO₃ instead of KOAc	Trace
3^d	None	0	9	Without PivOH	20
4	Without light or [Ru(p-cymene)Cl₂]₂ or Ar	0	10	(PhO)₂P(O)OH or BNDHP instead of PivOH	<10, 49
5	RuCl₃ instead of [Ru(p-cymene)Cl₂]₂	<10	11	MeOH or DMSO instead of 1,4-dioxane	Trace
6	Ru₃(CO)₁₂ instead of [Ru(p-cymene)Cl₂]₂	0	12	50 ℃ or 40 ℃ instead of 60 ℃	64, 68

Table 1. Optimization of the reaction conditionsa

Scheme 2. Substrate scope a Conversion in parentheses.

Scheme 3. Late-stage functionalization of material precursors and natural products

Scheme 4. Potential synthetic applications of 3a (a) (i) MeOTf (1.6 equiv.), toluene, 100 ℃, 2 h; (ii) CH3ONa (1.25 equiv.), MeOH, 80 ℃, 1 h. (b) [RhCl(cod)]2 (2.0 equiv.), PCy3 (30 mol%), B2(pin)2 (2.0 equiv.), toluene, 130 ℃, 15 h. (c) K2CO3 (2.0 equiv.), DMF, 120 ℃, 16 h.

Scheme 5. Mechanism studies

Scheme 6. Proposed mechanism

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光诱导钌催化苯酚衍生物间位选择性C—H烷基化反应