Facile scission of isonitrile carbon-nitrogen triple bond using a diborane(4) reagent.
Facile scission of isonitrile carbon-nitrogen triple bond using a diborane(4) reagent.
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DOI：
10.1038/ncomms5245
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发表时间：
2014-06-26
影响因子：
16.6
通讯作者：
Yamashita, Makoto
中科院分区：
文献类型：
--
作者：
Asakawa, Hiroki;Lee, Ka-Ho;Lin, Zhenyang;Yamashita, Makoto
过渡金属试剂和催化剂通常有效地裂解三键中的所有三个键（一个σ和两个π），尽管其具有高键能。最近，在没有过渡金属的情况下，通过使用主族元素化合物的单键断裂化学正在迅速发展。然而，使用非过渡金属化合物的三键的裂解较少探索。本文报道了一种不对称乙硼烷（4）化合物在室温下能与一氧化碳和叔丁基异腈反应。在后一种情况下，在不存在过渡金属的情况下，碳-氮三键被完全裂解，如通过X射线晶体学分析、具有13 C标记的13 C NMR光谱和DFT计算所证实的。DFT计算还揭示了详细的反应机理，并指出碳氮三键断裂的关键是其中一个中间体中存在亲核氮原子. 三键的断裂可以通过使用过渡金属催化剂来实现;然而，对于不含金属的体系，它还没有得到很好的探索。在这里，作者通过使用乙硼烷（4）试剂在温和条件下完全断裂了碳-氮三键。
Transition metal reagents and catalysts are generally effective to cleave all three bonds (one σ and two π) in a triple bond despite its high bonding energy. Recently, chemistry of single-bond cleavage by using main-group element compounds is rapidly being developed in the absence of transition metals. However, the cleavage of a triple bond using non-transition-metal compounds is less explored. Here we report that an unsymmetrical diborane(4) compound could react with carbon monoxide and tert-butyl isonitrile at room temperature. In the latter case, the carbon–nitrogen triple bond was completely cleaved in the absence of transition metal as confirmed by X-ray crystallographic analysis, 13C NMR spectroscopy with 13C labelling and DFT calculations. The DFT calculations also revealed the detailed reaction mechanism and indicated that the key for the carbon–nitrogen triple-bond cleavage could be attributed to the presence of nucleophilic nitrogen atom in one of the intermediates. The cleavage of triple bonds can be achieved through the use of transition metal catalysts; however, it is less well explored for metal-free systems. Here, the authors show complete cleavage of a carbon–nitrogen triple bond under mild conditions through the use of a diborane(4) reagent.
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影响因子：
15
作者：
Dobrovetsky, Roman;Stephan, Douglas W.
通讯作者：
Stephan, Douglas W.
影响因子：
16.6
作者：
Bonet, Amadeu;Gulyas, Henrik;Fernandez, Elena
通讯作者：
Fernandez, Elena
DOI：
10.1107/s010827010703569x
发表时间：
2007-10-01
期刊：
ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS
影响因子：
--
作者：
Clegg, William;Marder, Todd B.;Scott, Andrew. J.
通讯作者：
Scott, Andrew. J.
影响因子：
16.6
作者：
Braunschweig, Holger;Damme, Alexander;Radacki, Krzysztof
通讯作者：
Radacki, Krzysztof
影响因子：
4.6
作者：
Brown, Zachary D.;Power, Philip P.
通讯作者：
Power, Philip P.