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羧酸盐的无过渡金属脱羧烯基化反应

Transition metal-free decarboxylative olefination of carboxylic acid salts.

作者信息

Joseph Ebbin, Brar Deshkanwar S, Stuhlsatz Gaven, Tunge Jon A

机构信息

Department of Chemistry, The University of Kansas 1567 Irving Hill Road Lawrence Kansas USA

出版信息

Chem Sci. 2024 May 15;15(24):9353-9360. doi: 10.1039/d4sc01905a. eCollection 2024 Jun 19.

DOI:10.1039/d4sc01905a
PMID:38903232
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11186341/
Abstract

The cost-effective and efficient synthesis of alkenes is highly significant due to their extensive applications in both synthetic and polymer industries. A transition metal-free approach has been devised for the chemoselective olefination of carboxylic acid salts. This modular approach provides direct access to valuable electron-deficient styrenes in moderate to good yields. Detailed mechanistic studies suggest anionic decarboxylation is followed by halogen ion transfer. This halogen transfer leads to an umpolung of reactant electronics, allowing for a rate-limiting rebound elimination.

摘要

烯烃的经济高效合成具有重要意义，因为它们在合成和聚合物工业中都有广泛应用。已设计出一种无过渡金属的方法用于羧酸盐的化学选择性烯基化反应。这种模块化方法能够以中等至良好的产率直接获得有价值的缺电子苯乙烯。详细的机理研究表明，先是阴离子脱羧，然后是卤素离子转移。这种卤素转移导致反应物电子性质的反转，从而实现限速的反弹消除反应。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2c3c/11186341/4025181aed4d/d4sc01905a-s9.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2c3c/11186341/f5ce0519f89a/d4sc01905a-s8.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2c3c/11186341/4025181aed4d/d4sc01905a-s9.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2c3c/11186341/d2ab3c03d552/d4sc01905a-s1.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2c3c/11186341/be930e705e6a/d4sc01905a-s4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2c3c/11186341/19066f7b3fad/d4sc01905a-s5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2c3c/11186341/b6809ad54198/d4sc01905a-s6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2c3c/11186341/45d2ecbe5e1e/d4sc01905a-s7.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2c3c/11186341/f5ce0519f89a/d4sc01905a-s8.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2c3c/11186341/4025181aed4d/d4sc01905a-s9.jpg

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Scalable Electrochemical Decarboxylative Olefination Driven by Alternating Polarity.由交替极性驱动的可扩展电化学脱羧烯基化反应
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Rhodium-Catalyzed Asymmetric C-H Functionalization Reactions.铑催化的不对称碳氢键官能团化反应
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