Regioselective ring-opening of epoxides triggered by light

doi:10.1016/S1872-2067(26)65016-4

Abstract

Abstract:

Epoxides boast intrinsic ring strain and high reactivity towards various nucleophiles, thus rendering them fundamental building blocks in organic synthesis. Notably, the ring-opening of these readily available compounds offers a versatile strategy to produce a diverse array of valuable functionalized molecules, such as alcohols, carboxylic acids, olefins, etc. However, the conventional reaction systems for ring-opening typically rely on harmful agents or harsh conditions, which limit their applicability in complex molecule synthesis. Recent advancements in photocatalysis have emerged as a sustainable and promising alternative for precise cleavage of strained C−O bonds in epoxides under mild conditions, showcasing rapid development over the past decade. This mini-review examines the mechanisms and strategies for regioselective epoxide ring-opening triggered by varieties of nucleophiles based on photocatalysis, encompassing fundamental concepts of ring-opening, key factors influencing product regioselectivity and the potential impact of operando techniques and artificial intelligence on this field. The persistent challenges and potential trajectory in this dynamic domain are also critically discussed to foster further innovation.

Key words: Ring-opening, Epoxide, Photocatalysis, Regioselectivity, Green chemistry

Jing-Yu Li, Yi-Jun Xu. Regioselective ring-opening of epoxides triggered by light[J]. Chinese Journal of Catalysis, 2026, 85: 34-46.

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Photocatalytic epoxide alcoholysis
Catalyst	Light		T			Nucleophile		Substrate		Atmosphere			Regioselectivity (α:β) ^a			Rate (mmol/(g·h))		Ref.
Cs₃Bi₂Br₉	Xe lamp >420 nm		20 °C			i-PrOH		styrene oxide		Air			90% (α)			1.3		[6]
CuPd/TiO₂	Xe lamp		r.t.^b			MeOH		styrene oxide		Ar			>99% (α)			176		[29]
ZIS₁@CdS	Xe lamp >420 nm		40 °C			i-PrOH		styrene oxide		Air			>99% (α)			87		[5]
ZIS₁@CdS	Xe lamp >420 nm		40 °C			i-PrOH		epichlorohydrin		Air			>99% (β)			1.8		[5]
MS/ZIS	Xe lamp		50 °C			i-PrOH		styrene oxide		Air			>95% (α)			582.6		[7]
Photocatalytic epoxide deoxygenation
Catalyst	Light		T		Nucleophile		Substrate			Atmosphere		Yield (Selectivity)				AQY (wavelength)		Ref.
TiO₂	Xe lamp >300 nm		30 °C		i-PrOH		styrene oxide			N₂		95% (95%)				8.5% (300 nm)		[30]
Au/CeO₂	Halogen lamp		30 °C		i-PrOH		styrene oxide			Ar		20% (88%)				n/a^c		[36]
Photocatalytic epoxide hydrogenolysis
Catalyst	Light	T		Electron donor					HTC^d		Regioselectivity (α:β) ^a			Substrate	Atmosphere		Yield	Ref.
Pt₂/TiO₂	Xe lamp >300 nm	30 °C		i-PrOH					Pt		n/a			trans-stilbene oxide	N₂		>99%	[39]
Cp₂TiCl₂	green LED	r.t.		iPr₂NEt					methyl thioglycolate		>99% (α)			oxirane	Ar		85%	[31]
Au/TiO₂	365 nm	25 °C		THF^e					Pd(OAc)₂		>99% (α)			styrene oxide	N₂		49%	[53]
Cp₂Zr(OTf)₂·THF	blue LED	35 °C		Ir(4-MeO-ppy)₃					cyclohexadiene		80% (β)			styrene oxide	N₂		90%	[40]
VB₁₂	427 nm	r.t.		Zn/NH₄Cl					TRIP Thiol ^f		95% (β)			styrene oxide	N₂		84%	[41]
Photocatalytic epoxide carboxylation
Catalyst	Light	T		Electron donor					base		Substrate			atmosphere	regioselectivity (α:β)^a		Yield	Ref.
4CzTPN	blue LED	r.t.		DIPEA ^g					Cs₂CO₃		Aryl epoxides			CO₂	>99% (α)		75%	[17]
Photocatalytic epoxide arylation
Catalyst	Light	T		Substrate					Ligands		Nucleophile			Atmosphere	Regioselectivity (α:β)^a		Yield	Ref.
VB₁₂/NiCl₂	blue LED	r.t.		styrene oxide					n/a		I-Ar			N₂	>99% (β)		60%	[54]
Cp₂TiCl₂/NiBr₂	blue LED	r.t.		epoxybutane					t-Bu-terpy		I-Ar			N₂	>99% (β)		48%	[9]
Cp₂TiCl₂/NiBr₂	blue LED	r.t.		styrene oxide					2-pyridine-methanimine		I-Ar			N₂	>99% (α)		82%	[9]
4CzIPN/NiBr₂	blue LED	r.t.		styrene oxide					chiral bilm		I-Ar			N₂	>99% (β)		70%	[32]
Photocatalytic epoxide allylation
Catalyst	Light	T		substrate					Electron donor		Allylating reagent			Atmosphere	Regioselectivity		Yield	Ref.
4CzIPN/NiCl₂(bpy)	blue LED	r.t.		oxabenzon-orbornadienes					Et₃N		allyl acetate			N₂	n/a		70%	[10]
4CzIPN/ NiCl₂(bpy)	blue LED	r.t.		oxabenzon-orbornadienes					Et₃N		vinylic cyclic carbonates			N₂	n/a		69%	[10]

Photocatalytic epoxide alcoholysis
Catalyst	Light		T			Nucleophile		Substrate		Atmosphere			Regioselectivity (α:β) ^a			Rate (mmol/(g·h))		Ref.
Cs₃Bi₂Br₉	Xe lamp >420 nm		20 °C			i-PrOH		styrene oxide		Air			90% (α)			1.3		[6]
CuPd/TiO₂	Xe lamp		r.t.^b			MeOH		styrene oxide		Ar			>99% (α)			176		[29]
ZIS₁@CdS	Xe lamp >420 nm		40 °C			i-PrOH		styrene oxide		Air			>99% (α)			87		[5]
ZIS₁@CdS	Xe lamp >420 nm		40 °C			i-PrOH		epichlorohydrin		Air			>99% (β)			1.8		[5]
MS/ZIS	Xe lamp		50 °C			i-PrOH		styrene oxide		Air			>95% (α)			582.6		[7]
Photocatalytic epoxide deoxygenation
Catalyst	Light		T		Nucleophile		Substrate			Atmosphere		Yield (Selectivity)				AQY (wavelength)		Ref.
TiO₂	Xe lamp >300 nm		30 °C		i-PrOH		styrene oxide			N₂		95% (95%)				8.5% (300 nm)		[30]
Au/CeO₂	Halogen lamp		30 °C		i-PrOH		styrene oxide			Ar		20% (88%)				n/a^c		[36]
Photocatalytic epoxide hydrogenolysis
Catalyst	Light	T		Electron donor					HTC^d		Regioselectivity (α:β) ^a			Substrate	Atmosphere		Yield	Ref.
Pt₂/TiO₂	Xe lamp >300 nm	30 °C		i-PrOH					Pt		n/a			trans-stilbene oxide	N₂		>99%	[39]
Cp₂TiCl₂	green LED	r.t.		iPr₂NEt					methyl thioglycolate		>99% (α)			oxirane	Ar		85%	[31]
Au/TiO₂	365 nm	25 °C		THF^e					Pd(OAc)₂		>99% (α)			styrene oxide	N₂		49%	[53]
Cp₂Zr(OTf)₂·THF	blue LED	35 °C		Ir(4-MeO-ppy)₃					cyclohexadiene		80% (β)			styrene oxide	N₂		90%	[40]
VB₁₂	427 nm	r.t.		Zn/NH₄Cl					TRIP Thiol ^f		95% (β)			styrene oxide	N₂		84%	[41]
Photocatalytic epoxide carboxylation
Catalyst	Light	T		Electron donor					base		Substrate			atmosphere	regioselectivity (α:β)^a		Yield	Ref.
4CzTPN	blue LED	r.t.		DIPEA ^g					Cs₂CO₃		Aryl epoxides			CO₂	>99% (α)		75%	[17]
Photocatalytic epoxide arylation
Catalyst	Light	T		Substrate					Ligands		Nucleophile			Atmosphere	Regioselectivity (α:β)^a		Yield	Ref.
VB₁₂/NiCl₂	blue LED	r.t.		styrene oxide					n/a		I-Ar			N₂	>99% (β)		60%	[54]
Cp₂TiCl₂/NiBr₂	blue LED	r.t.		epoxybutane					t-Bu-terpy		I-Ar			N₂	>99% (β)		48%	[9]
Cp₂TiCl₂/NiBr₂	blue LED	r.t.		styrene oxide					2-pyridine-methanimine		I-Ar			N₂	>99% (α)		82%	[9]
4CzIPN/NiBr₂	blue LED	r.t.		styrene oxide					chiral bilm		I-Ar			N₂	>99% (β)		70%	[32]
Photocatalytic epoxide allylation
Catalyst	Light	T		substrate					Electron donor		Allylating reagent			Atmosphere	Regioselectivity		Yield	Ref.
4CzIPN/NiCl₂(bpy)	blue LED	r.t.		oxabenzon-orbornadienes					Et₃N		allyl acetate			N₂	n/a		70%	[10]
4CzIPN/ NiCl₂(bpy)	blue LED	r.t.		oxabenzon-orbornadienes					Et₃N		vinylic cyclic carbonates			N₂	n/a		69%	[10]