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二茂镁催化的胺硼烷脱氢偶联反应

Magnesocenophane-Catalyzed Amine Borane Dehydrocoupling.

作者信息

Wirtz Lisa, Haider Wasim, Huch Volker, Zimmer Michael, Schäfer André

机构信息

Faculty of Natural Science and Technology, Department of Chemistry, Saarland University, Campus Saarbrücken, 66123, Saarbrücken, Germany.

出版信息

Chemistry. 2020 May 15;26(28):6176-6184. doi: 10.1002/chem.202000106. Epub 2020 Apr 28.

DOI:10.1002/chem.202000106
PMID:32052880
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7318289/
Abstract

The Lewis acidities of a series of [n]magnesocenophanes (1 a-d) have been investigated computationally and found to be a function of the tilt of the cyclopentadienyl moieties. Their catalytic abilities in amine borane dehydrogenation/dehydrocoupling reactions have been probed, and C[1]magnesocenophane (1 a) has been shown to effectively catalyze the dehydrogenation/dehydrocoupling of dimethylamine borane (2 a) and diisopropylamine borane (2 b) under ambient conditions. Furthermore, the mechanism of the reaction with 2 a has been investigated experimentally and computationally, and the results imply a ligand-assisted mechanism involving stepwise proton and hydride transfer, with dimethylaminoborane as the key intermediate.

摘要

通过计算研究了一系列[n]镁茂（1 a-d）的路易斯酸性，发现其与环戊二烯基部分的倾斜度有关。研究了它们在胺硼烷脱氢/脱氢偶联反应中的催化能力，结果表明，在环境条件下，碳[1]镁茂（1 a）能有效催化二甲胺硼烷（2 a）和二异丙胺硼烷（2 b）的脱氢/脱氢偶联反应。此外，通过实验和计算研究了与2 a反应的机理，结果表明该反应为配体辅助机理，涉及质子和氢化物的逐步转移，二甲氨基硼烷为关键中间体。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/00ca/7318289/cf587bc8ff43/CHEM-26-6176-g010.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/00ca/7318289/cf587bc8ff43/CHEM-26-6176-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/00ca/7318289/2747c6d8ac26/CHEM-26-6176-g001.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/00ca/7318289/163ab11e9035/CHEM-26-6176-g011.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/00ca/7318289/150103514d25/CHEM-26-6176-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/00ca/7318289/eb0c383455e3/CHEM-26-6176-g013.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/00ca/7318289/737cf915d482/CHEM-26-6176-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/00ca/7318289/1ddd8840a004/CHEM-26-6176-g014.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/00ca/7318289/4d8ad1064267/CHEM-26-6176-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/00ca/7318289/52577fb11d92/CHEM-26-6176-g015.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/00ca/7318289/76c3a8c46149/CHEM-26-6176-g016.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/00ca/7318289/b091011c5129/CHEM-26-6176-g017.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/00ca/7318289/697a19c3e3cc/CHEM-26-6176-g018.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/00ca/7318289/cf587bc8ff43/CHEM-26-6176-g010.jpg

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