Borylnitrenes: electrophilic reactive intermediates with high reactivity towards C-H bonds
Borylnitrenes: electrophilic reactive intermediates with high reactivity towards C-H bonds
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DOI：
10.1039/c0ob00107d
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发表时间：
2010-01-01
影响因子：
3.2
通讯作者：
Filthaus, Matthias
中科院分区：
文献类型：
--
作者：
Bettinger, Holger F.;Filthaus, Matthias
硼基氮烯（catBN 3a 和 pinBN 3b；cat = 儿茶酚，pin = pinacolato）是反应性中间体，表现出高度插入未活化烃的 C-H 键的趋势。本文总结了旨在通过光谱手段识别、表征和研究 3a 的化学行为的基质分离研究，以及使用 3b 在溶液和气相中进行的实验。与报道的二氟亚乙烯基 1a 在固体氩中的反应性比较表明，3a 显示出大体相似的反应性，但仅在光化学激发后。衍生物3b以高产率插入烃溶剂的C-H键，从而允许从“非反应性”烃形成伯胺、仲胺或酰胺。也可用于室温下气相甲烷生成甲胺或甲酰胺。简要总结了硼基氮烯化学中剩余的挑战。
Borylnitrenes (catBN 3a and pinBN 3b; cat = catecholato, pin = pinacolato) are reactive intermediates that show high tendency towards insertion into the C-H bonds of unactivated hydrocarbons. The present article summarizes the matrix isolation investigations that were aimed at identifying, characterizing and investigating the chemical behaviour of 3a by spectroscopic means, and of the experiments in solution and in the gas phase that were performed with 3b. Comparison with the reactivity reported for difluorovinylidene 1a in solid argon indicates that 3a shows by and large similar reactivity, but only after photochemical excitation. The derivative 3b inserts into the C-H bonds of hydrocarbon solvents in high yields and thus allows the formation of primary amines, secondary amines, or amides from "unreactive" hydrocarbons. It can also be used for generation of methylamine or methylamide from methane in the gas phase at room temperature. Remaining challenges in the chemistry of borylnitrenes are briefly summarized.