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碘代烯烃的Negishi型同偶联反应中的意外异构化

Unexpected -to- Isomerizations during the Negishi-Type Homocoupling of Iodoalkenes.

作者信息

Crovara Fernanda A, Martí Josep, Costa Anna M, Vilarrasa Jaume

机构信息

Organic Chemistry Section, Facultat de Química, Universitat de Barcelona, Diagonal 645, 08028 Barcelona, Catalonia, Spain.

出版信息

J Org Chem. 2024 Oct 4;89(19):14483-14488. doi: 10.1021/acs.joc.3c02957. Epub 2024 Sep 17.

DOI:10.1021/acs.joc.3c02957
PMID:39287987
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11580178/
Abstract

The direct insertion of Zn into olefin-halide bonds is a challenge. When ()-alkenyl iodides were treated with a very large excess of Zn nanoparticles, in the presence of Pd(PPh), the dimerization was observed but, unexpectedly, yielding mainly -1,3-dienes. This apparently contrathermodynamic -to- isomerization of organometallic intermediates is predicted to be general and is explained with the aid of DFT [principally M06/6-311+G(d,p)], MP2, and CCSD(T) calculations.

摘要

将锌直接插入烯烃-卤化物键是一项挑战。当（）-链烯基碘化物在大量过量的锌纳米颗粒存在下，用Pd(PPh)处理时，观察到二聚反应，但出乎意料的是，主要生成-1,3-二烯。这种有机金属中间体明显违反热力学的异构化预计是普遍现象，并借助密度泛函理论（主要是M06/6-311+G(d,p)）、二阶微扰理论（MP2）和耦合簇单双激发理论（CCSD(T)）计算进行了解释。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c2e9/11580178/6e57cda438b9/jo3c02957_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c2e9/11580178/cbb83a59e8f5/jo3c02957_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c2e9/11580178/a4953cb916e9/jo3c02957_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c2e9/11580178/55bbe58ccfc5/jo3c02957_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c2e9/11580178/be6592bbb733/jo3c02957_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c2e9/11580178/6e57cda438b9/jo3c02957_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c2e9/11580178/cbb83a59e8f5/jo3c02957_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c2e9/11580178/a4953cb916e9/jo3c02957_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c2e9/11580178/55bbe58ccfc5/jo3c02957_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c2e9/11580178/be6592bbb733/jo3c02957_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c2e9/11580178/6e57cda438b9/jo3c02957_0005.jpg

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