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用于末端炔烃选择性脱氢硼化反应的两种氢化锌预催化剂的比较:详细的机理研究

Comparison of Two Zinc Hydride Precatalysts for Selective Dehydrogenative Borylation of Terminal Alkynes: A Detailed Mechanistic Study.

作者信息

Sahoo Rajata Kumar, Patro Arukela Ganesh, Sarkar Nabin, Nembenna Sharanappa

机构信息

School of Chemical Sciences, National Institute of Science Education and Research (NISER), Homi Bhabha National Institute (HBNI), Bhubaneswar 752 050, India.

出版信息

ACS Omega. 2023 Jan 10;8(3):3452-3460. doi: 10.1021/acsomega.2c07381. eCollection 2023 Jan 24.

DOI:10.1021/acsomega.2c07381
PMID:36713704
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9878541/
Abstract

The conjugated bis-guanidinate-stabilized zinc hydride complex ()-precatalyzed chemoselective dehydroborylation of a wide array of terminal alkynes with excellent yields is reported. Further, precatalyst is compared with a newly synthesized NacNac zinc hydride precatalyst () for selective dehydroborylation of terminal alkynes, and it is discovered that precatalyst is more active than . We have studied intra- and intermolecular chemoselective dehydroborylation of terminal alkynes over other reducible functionalities such as alkene, ester, isocyanide, nitro, and heterocycles. The highly efficient precatalyst shows a turnover number of 48.5 and turnover frequency of up to 60.5 h in the dehydroborylation of 1-ethynyl-4-fluorobenzene (). A plausible mechanism for selective dehydrogenative borylation of alkynes has been proposed based on active catalyst isolation and a series of stoichiometric reactions.

摘要

据报道,共轭双胍稳定的氢化锌配合物()能高效地预催化多种末端炔烃的化学选择性脱氢硼化反应,产率优异。此外,将预催化剂与新合成的NacNac氢化锌预催化剂()用于末端炔烃的选择性脱氢硼化反应进行比较,发现预催化剂比更具活性。我们研究了末端炔烃相对于其他可还原官能团(如烯烃、酯、异氰化物、硝基和杂环)的分子内和分子间化学选择性脱氢硼化反应。高效的预催化剂在1-乙炔基-4-氟苯()的脱氢硼化反应中显示出48.5的周转数和高达60.5 h的周转频率。基于活性催化剂的分离和一系列化学计量反应,提出了一种合理的炔烃选择性脱氢硼化反应机理。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/566e/9878541/4046c0280981/ao2c07381_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/566e/9878541/02344f8b1fa6/ao2c07381_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/566e/9878541/2c878bfe9c16/ao2c07381_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/566e/9878541/1c31d7dc243c/ao2c07381_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/566e/9878541/67bd7f90ce8a/ao2c07381_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/566e/9878541/1a56a99b0c2e/ao2c07381_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/566e/9878541/4046c0280981/ao2c07381_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/566e/9878541/02344f8b1fa6/ao2c07381_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/566e/9878541/2c878bfe9c16/ao2c07381_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/566e/9878541/1c31d7dc243c/ao2c07381_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/566e/9878541/67bd7f90ce8a/ao2c07381_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/566e/9878541/1a56a99b0c2e/ao2c07381_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/566e/9878541/4046c0280981/ao2c07381_0007.jpg

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