Catalytic C-N, C-O, and C-S Bond Formation Promoted by Organoactinide Complexes
Catalytic C-N, C-O, and C-S Bond Formation Promoted by Organoactinide Complexes
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DOI：
10.1007/978-3-642-12073-2_7
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发表时间：
2010-01-01
期刊：
影响因子：
--
通讯作者：
Eisen, Moris S.
中科院分区：
文献类型：
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作者：
Eisen, Moris S.
在过去的十年中，我们已经目睹了亲电的d（0）/f（n）锕系元素的化学是如何令人印象深刻地发展的，无论是在它们的新合成方法中获得非常有趣的化合物，还是在它们在化学计量和催化反应中的应用中导致高度的复杂性。有机锕系元素独特的、丰富的和复杂的特征促使这一领域朝着催化要求高的化学转化的方向发展。本文综述了近年来有机锕系元素配合物均相催化的研究进展，特别是在C-N，C-O和C-S键的形成方面。我们首先介绍了相应的有机锕系配合物的合成和表征，然后是均相催化化学转化，包括末端炔的氢胺化，E-己内酯和L-丙交酯的聚合，叠氮化物和肼的还原高价有机硫脲配合物，末端炔的氢硫醇化，和催化Tishchenko反应。对于每个反应，范围和热力学，动力学和机械方面。
Throughout this last decade, we have witnessed impressively how the chemistry of electrophilic d(0)/f(n) actinides has been prospering either in their new synthetic approaches reaching very interesting compounds or in their use in stoichiometric and catalytic reactions leading to high levels of complexity. The unique rich and complex features of organoactinides prompted the development of this field toward catalysis in demanding chemical transformations. In this review, we present a brief and selective survey of the recent developments in homogenous catalysis of organoactinide complexes, especially toward the formation of new C-N, C-O, and C-S bonds. We start by presenting the synthesis and characterization of the corresponding organoactinide complexes, followed by the homogeneous catalytic chemical transformations that include the hydroamination of terminal alkynes, the polymerization of E-caprolactone and L-lactide, the reduction of azides and hydrazines by high-valent organouranium complexes, the hydrothiolation of terminal alkynes, and the catalytic Tishchenko reaction. For each reaction, the scope and the thermodynamic, kinetic, and mechanistic aspects are presented.