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NHC-金催化的炔丙基硼酸频哪醇酯异构化为丙二烯以及炔烃双重异构化为1,3-二烯

NHC-Au-Catalyzed Isomerization of Propargylic B(MIDA)s to Allenes and Double Isomerization of Alkynes to 1,3-Dienes.

作者信息

Liu Li-Cai, Lin Shuang, Xu Kangwei, Qian Jiasheng, Wu Ruibo, Li Qingjiang, Wang Honggen

机构信息

Guangdong Provincial Key Laboratory of Chiral Molecule and Drug Discovery, School of Pharmaceutical Sciences, Sun Yat-Sen University, Guangzhou, 510006, China.

出版信息

Adv Sci (Weinh). 2024 Jun;11(21):e2308710. doi: 10.1002/advs.202308710. Epub 2024 Mar 13.

DOI:10.1002/advs.202308710
PMID:38477453
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11151053/
Abstract

The synthesis of allenyl boronates is an important yet challenging topic in organic synthesis. Reported herein is an NHC-gold-catalyzed 1,3-H shift toward allenyl boronates synthesis from simple propargylic B(MIDA)s. Mechanistic studies suggest dual roles of the boryl moiety in the reaction: to activate the substrate for isomerization and at the same time, to prevent the allene product from further isomerization. These effects should be a result of α-anion stabilization and α-cation destabilization conferred by the B(MIDA) moiety, respectively. The NHC-Au catalyst, which is commercially available, is also found to be reactive in alkyne-to-1,3-diene isomerization reactions in an atom-economic and base-free manner.

摘要

联烯硼酸酯的合成是有机合成中一个重要但具有挑战性的课题。本文报道了一种NHC-金催化的从简单的炔丙基硼酸酯通过1,3-氢迁移合成联烯硼酸酯的方法。机理研究表明硼基部分在反应中具有双重作用：激活底物进行异构化，同时防止联烯产物进一步异构化。这些效应分别是由B(MIDA)部分赋予的α-阴离子稳定化和α-阳离子去稳定化的结果。还发现市售的NHC-Au催化剂在炔烃到1,3-二烯的异构化反应中具有活性，且具有原子经济性和无需碱的特点。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2918/11151053/3e16352b5aa6/ADVS-11-2308710-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2918/11151053/7e0025ddfef2/ADVS-11-2308710-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2918/11151053/9db554de26a2/ADVS-11-2308710-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2918/11151053/9aa53738040e/ADVS-11-2308710-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2918/11151053/3dd865e6f1e5/ADVS-11-2308710-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2918/11151053/3e16352b5aa6/ADVS-11-2308710-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2918/11151053/7e0025ddfef2/ADVS-11-2308710-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2918/11151053/9db554de26a2/ADVS-11-2308710-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2918/11151053/9aa53738040e/ADVS-11-2308710-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2918/11151053/3dd865e6f1e5/ADVS-11-2308710-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2918/11151053/3e16352b5aa6/ADVS-11-2308710-g005.jpg

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本文引用的文献

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