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受阻路易斯酸碱对化学:探寻新反应

Frustrated Lewis Pair Chemistry: Searching for New Reactions.

作者信息

Kehr Gerald, Erker Gerhard

机构信息

Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, 48149 Münster, Corrensstr. 40, Germany.

出版信息

Chem Rec. 2017 Aug;17(8):803-815. doi: 10.1002/tcr.201700010. Epub 2017 Apr 12.

Abstract

Frustrated Lewis pair chemistry has taken a steep development in the recent years. It offers possibilities of developing new variants of known reactions and of finding new chemical transformations. This is demonstrated and described by the recently developed FLP-formylborane chemistry, which has led to the formation of the unique (η -formylborane)FLP adducts and opened a way of preparing a genuine formylborane compound, which shows an interesting follow-up chemistry. FLPs have helped finding phosphorus analogues of the enamine Stork reaction and the Claisen reaction. These reactions lead to new organophosphorus compounds and they make new phosphane/borane systems available. P/B FLPs add to a variety of small main group element oxides. They undergo 1,2-addition reactions to CO , SO and other heterocumulenes and they feature unique 1,1-addition reactions to carbon monoxide, to isonitriles and even to nitric oxide (NO), the latter yielding examples of a new class of persistent nitroxide radicals, the FLPNO nitroxyls. Eventually, some remarkable radical reactions of FLPs and related compounds are briefly mentioned.

摘要

受阻路易斯酸碱对化学近年来取得了迅猛发展。它为开发已知反应的新变体以及发现新的化学转化提供了可能性。最近发展的FLP-甲酰硼烷化学对此进行了展示和描述,该化学已导致形成独特的(η-甲酰硼烷)FLP加合物,并开辟了一条制备真正的甲酰硼烷化合物的途径,该化合物展现出有趣的后续化学性质。受阻路易斯酸碱对有助于找到烯胺斯托克反应和克莱森反应的磷类似物。这些反应生成新的有机磷化合物,并提供了新的膦/硼烷体系。P/B受阻路易斯酸碱对可与多种小主族元素氧化物加成。它们对CO、SO和其他连烯进行1,2-加成反应,并且对一氧化碳、异腈甚至一氧化氮(NO)具有独特的1,1-加成反应,后者产生了一类新型持久性氮氧自由基的实例,即FLPNO硝酰基。最后,简要提及了受阻路易斯酸碱对和相关化合物的一些显著的自由基反应。

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