C(sp3)H alkylation using H2O catalyst for hydrogen atom transfer over Ag-loaded TiO2 photocatalysis

IF 1.5 4区化学 Q3 CHEMISTRY, ORGANIC

Tetrahedron Letters Pub Date : 2025-07-25 DOI:10.1016/j.tetlet.2025.155766

Yuji Sakai , Buddhini P. Ranasinghe , Shogo Mori , Susumu Saito

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Abstract

We report the direct C(sp³)H bond alkylation using interfacial H₂O-covered, Ag nanoparticle-loaded TiO₂ (H₂O@Ag/TiO₂) semiconductor photocatalyst, where H₂O catalyst induces hydrogen atom transfer (HAT) without wasteful by-products. For the efficient and selective transformation, it is critical to use a mixed solvent system composed of CH₃CN and H₂O in an appropriate ratio and to employ relatively electrophilic alkenes as alkylating agents. A wide range of ethers were alkylated selectively at their α-C(sp³)H bonds adjacent to the oxygen atoms in good to excellent yields, regardless of their water affinities (water-miscible or poorly water-soluble), molecular frameworks (cyclic or acyclic), or physical states (liquid or solid). Cyclohexane with no ethereal oxygen, which is almost entirely immiscible with water, also underwent the C(sp³)H alkylation under a similar H₂O@Ag/TiO₂-photocatalyzed system.

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用H2O催化剂催化C(sp3)H烷基化，在负载ag的TiO2上进行氢原子转移

我们报道了使用H2O覆盖界面，Ag纳米粒子负载TiO2 （H2O@Ag/TiO2）半导体光催化剂直接进行C（sp3）氢键烷基化，其中H2O催化剂诱导氢原子转移（HAT）而不会产生浪费的副产物。为了实现高效和选择性的烷基化反应，关键是要使用合适比例的CH3CN和H2O组成的混合溶剂体系，并使用相对亲电的烯烃作为烷基化剂。许多醚在氧原子附近的α-C（sp3）氢键上选择性地烷基化，收率从高到高不等，而不考虑它们的水亲和性（与水混溶或难溶于水）、分子框架（环或非环）或物理状态（液体或固体）。不含乙醛氧的环己烷几乎完全不与水混溶，在类似H2O@Ag/ tio2光催化体系下也发生了C(sp3)H烷基化反应。

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来源期刊

Tetrahedron Letters 化学-有机化学

CiteScore

3.50

自引率

5.60%

发文量

521

审稿时长

28 days

期刊介绍： Tetrahedron Letters provides maximum dissemination of outstanding developments in organic chemistry. The journal is published weekly and covers developments in techniques, structures, methods and conclusions in experimental and theoretical organic chemistry. Rapid publication of timely and significant research results enables researchers from all over the world to transmit quickly their new contributions to large, international audiences.