Development of Ir(III) Photocatalysts Enabling Blue-Light-Induced Hydrocarboxylation of Unactivated Alkenes and Arenes.

IF 5 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Letters Pub Date : 2025-10-15 DOI:10.1021/acs.orglett.5c03839

Jun-Qin Peng,Qiang Liu,Fu-Min Zhang,Xiao-Ming Zhang,Ka Lu,Bao-Sheng Li,Yong-Qiang Tu

引用次数: 0

Abstract

Novel types of CCC pincer Ir(III) organometallics with ligands of flexible seven-membered ring N-heterocyclic carbene (NHC) and 1,4-diimine are designed and developed as photocatalysts (PC1-PC3), which show the characteristic maximum absorption at the farther blue light region (λabs = 485-499 nm) than the usual commercial Ir(III) catalysts. Photocatalytic hydrocarboxylation using PC1 and PC2 with HCO2Cs under irradiation of blue LEDs has proven to be well-effective particularly toward unactivated internal alkenes and arenes, presenting a broad scope (>50 examples) and up to 95% yields and >20:1 regioselectivity as well. A mechanistic study proposes a photocatalytic process, which involves hydrogen atom transfer (HAT) and O-Ir(III) homolysis to generate the active Ir(III)-H species for catalytic cycling. This achievement offers a valuable example for possibly exploring the more potential photocatalytic reactivity of this system.

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蓝光诱导非活化烯烃和芳烃羟基化的Ir（III）光催化剂的研制。

以柔性七元环n-杂环碳（NHC）和1,4-二亚胺为配体的新型CCC钳形Ir（III）有机金属材料作为光催化剂（PC1-PC3），在更远的蓝光区（λabs = 485-499 nm）表现出比通常的商用Ir（III）催化剂的最大吸收特征。在蓝色led的照射下，PC1和PC2与HCO2Cs的光催化羧化反应已被证明是非常有效的，特别是对未活化的内部烯烃和芳烃，具有广泛的范围（bbb50个例子），高达95%的产率和>20:1的区域选择性。机理研究提出了一种光催化过程，该过程涉及氢原子转移（HAT）和O-Ir（III）均解，产生活性Ir(III)-H物质进行催化循环。这一成果为探索该体系更潜在的光催化活性提供了一个有价值的例子。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Organic Letters 化学-有机化学

CiteScore

9.30

自引率

11.50%

发文量

1607

审稿时长

1.5 months

期刊介绍： Organic Letters invites original reports of fundamental research in all branches of the theory and practice of organic, physical organic, organometallic,medicinal, and bioorganic chemistry. Organic Letters provides rapid disclosure of the key elements of significant studies that are of interest to a large portion of the organic community. In selecting manuscripts for publication, the Editors place emphasis on the originality, quality and wide interest of the work. Authors should provide enough background information to place the new disclosure in context and to justify the rapid publication format. Back-to-back Letters will be considered. Full details should be reserved for an Article, which should appear in due course.