Dual Photoexcited Palladium and Photoredox-Catalyzed Remote C(sp3)–H Acylation of Hydroxyamides

IF 5 1区 化学 Q1 CHEMISTRY, ORGANIC
Daling Li, Jun Wei, Lixu Ren, Lingmin Zhou, Liya Huang, Ying Yu, Siping Wei, Na Hao, Jun Wang, Lin Yang, Xianchao Pan, Qiang Fu, Ji Lu
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引用次数: 0

Abstract

Herein, we report an unprecedented dual photoexcited palladium and photoredox-catalyzed remote C(sp3)–H acylation of amides free of external acylating reagents through sequential N–O/C–H/C–O bond cleavage and chemoselective C–C bond formation. This dual catalytic system shows high efficiency, good atom economy by deletion of oxygen, and diverse functional group tolerance. Experimental investigation of the reaction mechanism revealed that O-acyl hydroxamides enabled by photoexcited palladium generated the alkyl radicals via a 1,5-HAT process mediated by amidyl radicals and a palladium carboxylate complex, which, undergoing photoredox-catalyzed phosphoranyl radical-mediated C–O bond cleavage, leads to coupling with alkyl radicals to deliver the final products.

Abstract Image

双光激发钯和光氧化还原催化远端C(sp3) -H酰化羟基酰胺
在此,我们报道了一个前所未有的双光激发钯和光氧化还原催化的酰胺的远程C(sp3) -H酰化,通过顺序的N-O /C -H /C - o键裂解和化学选择性的C - C键形成,而不需要外部酰化试剂。该双催化体系具有效率高、删氧原子经济性好、官能团耐受性强等特点。对反应机理的实验研究表明,由光激发钯激活的o -酰基羟酰胺通过氨基自由基和钯羧酸配合物介导的1,5- hat过程产生烷基自由基,该配合物经过光氧化还原催化的磷酰自由基介导的C-O键裂解,导致与烷基自由基偶联以传递最终产物。
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来源期刊
Organic Letters
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.
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