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易于获取膦硼烷结构单元。

Easy Access to Phosphine-Borane Building Blocks.

作者信息

de Jong G Bas, Ortega Nuria, Lutz Martin, Lammertsma Koop, Slootweg J Chris

机构信息

Van't Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam, P.O. Box 94157, 1090 GD, Amsterdam, The Netherlands.

Faculty of Sciences, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands.

出版信息

Chemistry. 2020 Dec 4;26(68):15944-15952. doi: 10.1002/chem.202002367. Epub 2020 Oct 23.

DOI:10.1002/chem.202002367
PMID:32602582
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7756754/
Abstract

In this paper, we highlight the synthesis of a variety of primary phosphine-boranes (RPH ⋅BH ) from the corresponding dichlorophosphines, simply by using Li[BH ] as reductant and provider of the BH protecting group. The method offers facile access not only to alkyl- and arylphosphine-boranes, but also to aminophosphine-boranes (R NPH ⋅BH ) that are convenient building blocks but without the protecting BH moiety thermally labile and notoriously difficult to handle. The borane-protected primary phosphines can be doubly deprotonated using n-butyllithium to provide soluble phosphanediides Li [RP⋅BH ] of which the phenyl-derivative Li [PhP⋅BH ] was structurally characterized in the solid state.

摘要

在本文中,我们着重介绍了由相应的二氯膦出发,仅使用Li[BH₄]作为还原剂和BH保护基团的提供者来合成多种伯膦硼烷(RPH₂·BH₃)的方法。该方法不仅能便捷地合成烷基和芳基膦硼烷,还能合成氨基膦硼烷(R₂NPH₂·BH₃),它们是便利的结构单元,但其中的BH保护部分热不稳定且 notoriously difficult to handle(此处原文有误,结合语境推测可能是“notoriously difficult to handle”,意为“极其难以处理”)。硼烷保护的伯膦可以用正丁基锂进行双去质子化,以提供可溶性的膦二负离子Li₂[RP·BH₂],其中苯基衍生物Li₂[PhP·BH₂]的固态结构已得到表征。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/392e/7756754/707de5e78ca9/CHEM-26-15944-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/392e/7756754/ed36aef61fbc/CHEM-26-15944-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/392e/7756754/e7de52f176f3/CHEM-26-15944-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/392e/7756754/cf7982ee6d96/CHEM-26-15944-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/392e/7756754/b1308fbcd484/CHEM-26-15944-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/392e/7756754/d3b6aef203c9/CHEM-26-15944-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/392e/7756754/48799150658d/CHEM-26-15944-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/392e/7756754/707de5e78ca9/CHEM-26-15944-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/392e/7756754/ed36aef61fbc/CHEM-26-15944-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/392e/7756754/e7de52f176f3/CHEM-26-15944-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/392e/7756754/cf7982ee6d96/CHEM-26-15944-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/392e/7756754/b1308fbcd484/CHEM-26-15944-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/392e/7756754/d3b6aef203c9/CHEM-26-15944-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/392e/7756754/48799150658d/CHEM-26-15944-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/392e/7756754/707de5e78ca9/CHEM-26-15944-g005.jpg

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本文引用的文献

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Nat Commun. 2019 Mar 26;10(1):1370. doi: 10.1038/s41467-019-08967-8.
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2,6-二甲基苯基膦铷盐和铯盐固态结构中的结构多样性
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