Visible-Light Photocatalytic Aerobic C═C Bond Cleavage of Alkenes to Carbonyls by CsPbBr₃ Nanocrystals

Abstract

Herein, we reported a facile and readily accessible visible-light-driven photocatalytic protocol to induce oxidative cleavage of C�C bonds to corresponding carbonyls using CsPbBr 3 nanocrystals as photocatalysts. This catalytic system was applicable to a wide range of terminal and internal alkenes. Detailed mechanism studies indicated that a single-electron transfer (SET) process was involved in this transformation, wherein the superoxide radical (O 2•− ) and photogenerated holes played crucial roles. Additionally, DFT calculations revealed that the reaction was initiated by the addition of O 2•− to the terminal carbon atom of the C�C bond and completed by releasing one molecular formaldehyde by the formed [2 + 2] intermediate; the latter conversion was a rate-determining process.

Recent Advances in Photoinduced Oxidative Cleavage of Alkenes

“…Similarly, Le and co-workers presented a facile visible-lightdriven photocatalytic protocol using CsPbBr 3 nanocrystals to cleave alkenes, yielding carbonyls. 40 A range of terminal and internal alkenes were amenable under this protocol. The CsPbBr 3 catalytic system occurs via an ET route to generate the dioxetane intermediate which fragments to give the final carbonyl products.…”

Visible-Light Photocatalytic Highly Selective Oxidation of Alcohols into Carbonyl Compounds by CsPbBr3 Perovskite

“…In the past 5 years, the application of CsPbBr 3 nanomaterials in catalyzing organic reactions have attracted increasing attention due to their outstanding photoelectrical properties, which have been used to catalyze the coupling reaction, C–H activation, and α-alkylation of aldehyde . Lately, our group used the CsPbBr 3 nanomaterial as a visible-light photocatalyst to successfully realize the oxidation reaction of various alkenes, amines, and sulfides . Nevertheless, compared with other semiconductor materials, the application of CsPbBr 3 in organic synthesis is far from being fully developed.…”

Insights into interfacial mechanisms: CsPbBr3 nanocrystals as sustainable photocatalysts for primary amine oxidation

“…3 While inorganic LHPs, primarily CsPbBr 3 , have been favored for organic transformations due to their suitable band gap and robust chemical stability under reaction conditions, the potential of surface interactions between these perovskites and reactant molecules remains untapped. 3,16–22 Exploring these interactions offers a pathway to unveil mechanistic insights, enhance reaction yields, and fine-tune selectivity. Primary amines, as reactants, are particularly intriguing due to their specific interactions with perovskite surfaces.…”