Direct 1,2-Dicarbonylation of Alkenes towards 1,4-Diketones via Photocatalysis

被引:56
作者
Cheng, Yuan-Yuan [1 ,2 ]
Yu, Ji-Xin [1 ,2 ]
Lei, Tao [1 ,2 ]
Hou, Hong-Yu [1 ,2 ]
Chen, Bin [1 ,2 ]
Tung, Chen-Ho [1 ,2 ]
Wu, Li-Zhu [1 ,2 ]
机构
[1] Chinese Acad Sci, Tech Inst Phys & Chem, Key Lab Photochem Convers & Optoelect Mat, Beijing 100190, Peoples R China
[2] Univ Chinese Acad Sci, Sch Future Technol, Beijing 100049, Peoples R China
基金
中国国家自然科学基金;
关键词
alkenes; diacylation; photocatalysis; reaction mechanisms; synthetic methods; C-H BORYLATION; 1,4-DICARBONYL COMPOUNDS; CATALYZED FLUORINATION; PHOTOREDOX CATALYSIS; CONJUGATE ADDITION; STETTER REACTION; ACYLATION; METAL; ACIDS; HYDROACYLATION;
D O I
10.1002/anie.202112370
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
1,4-Dicarbonyl compounds are intriguing motifs and versatile precursors in numerous pharmaceutical molecules and bioactive natural compounds. Direct incorporation of two carbonyl groups into a double bond at both ends is straightforward, but also challenging. Represented herein is the first example of 1,2-dicarbonylation of alkenes by photocatalysis. Key to success is that N(n-Bu)(4)(+) not only associates with the alkyl anion to avoid protonation, but also activates the alpha-keto acid to undergo electrophilic addition. The alpha-keto acid is employed both for acyl generation and electrophilic addition. By tuning the reductive and electrophilic ability of the acyl precursor, unsymmetric 1,4-dicarbonylation is achieved for the first time. This metal-free, redox-neutral and regioselective 1,2-dicarbonylation of alkenes is executed by a photocatalyst for versatile substrates under extremely mild conditions and shows great potential in biomolecular and drug molecular derivatization.
引用
收藏
页码:26822 / 26828
页数:7
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