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Tandem Hydroaminomethylation Reaction to Synthesize Amines from Alkenes
Chemical Reviews ( IF 51.4 ) Pub Date : 2018-03-01 00:00:00 , DOI: 10.1021/acs.chemrev.7b00667 Philippe Kalck 1 , Martine Urrutigoïty 1
Chemical Reviews ( IF 51.4 ) Pub Date : 2018-03-01 00:00:00 , DOI: 10.1021/acs.chemrev.7b00667 Philippe Kalck 1 , Martine Urrutigoïty 1
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In the context of atom economy and low environmental impact, synthesis of amines by an efficient catalytic process is of great importance to produce these building blocks for fine chemical industry. The one-pot hydroaminomethylation of alkenes is a tandem reaction which involves three successive steps under CO/H2 pressure to perform the catalyzed hydroformylation of the alkene into the corresponding aldehyde followed by its condensation with a N–H function and the catalyzed hydrogenation of the imine/enamine intermediate into the corresponding saturated amine. Rhodium and more recently ruthenium complexes have been designed to combine high conversions of the reactants and chemoselectivity in the expected amines with high regioselectivity in either the linear or the branched amine. The coordination sphere of the metal according to the presence of ligands, temperature, CO/H2 partial pressures, and nature of the solvent is essential for complying with these selectivity requirements. The rate of the hydroformylation step needs to be fast with regard to the hydrogenation step. The role of amines in the coordination sphere and water, presumably in the second sphere, on the mechanism requires some more studies. Similarly, the enantioselective synthesis of amine is not yet achieved directly and interrupted processes or use of asymmetric organo-catalyzed reductive amination are efficient synthetic ways for producing chiral amines. The separation of the catalyst from the organic products by biphasic or (semi-) heterogeneized systems and its recycling have been demonstrated in many cases. The present review provides a report of the state of the art in this autotandem hydroaminomethylation catalysis and should open prospects in the design of less expensive and abundant metal complexes for reaching at low cost similar and even superior performances.
中文翻译：
串联氢氨基甲基化反应从烯烃合成胺
在原子经济和对环境的低影响的背景下，通过有效的催化过程合成胺对于生产用于精细化工的这些结构单元非常重要。烯烃的一锅法氢氨基甲基化是串联反应，涉及在CO / H 2下的三个连续步骤进行烯烃催化加氢甲酰化为相应的醛，然后将其缩合为N–H官能团，然后将亚胺/烯胺中间体催化加氢为相应的饱和胺。铑和最近的钌配合物已被设计为将反应物的高转化率和预期胺的化学选择性与直链或支链胺的高区域选择性结合在一起。根据配体的存在，温度，CO / H 2决定金属的配位范围分压和溶剂的性质对于满足这些选择性要求至关重要。相对于氢化步骤，加氢甲酰化步骤的速率需要快速。胺在配位领域和水（大概在第二个领域）对机理的作用还需要进一步研究。类似地，胺的对映选择性合成尚不能直接实现，中断的工艺或使用不对称的有机催化的还原胺化反应是生产手性胺的有效合成方法。在许多情况下，已经证明了通过双相或（半）异质化系统将催化剂从有机产物中分离出来并进行再循环。
更新日期：2018-03-01
中文翻译：
串联氢氨基甲基化反应从烯烃合成胺
在原子经济和对环境的低影响的背景下，通过有效的催化过程合成胺对于生产用于精细化工的这些结构单元非常重要。烯烃的一锅法氢氨基甲基化是串联反应，涉及在CO / H 2下的三个连续步骤进行烯烃催化加氢甲酰化为相应的醛，然后将其缩合为N–H官能团，然后将亚胺/烯胺中间体催化加氢为相应的饱和胺。铑和最近的钌配合物已被设计为将反应物的高转化率和预期胺的化学选择性与直链或支链胺的高区域选择性结合在一起。根据配体的存在，温度，CO / H 2决定金属的配位范围分压和溶剂的性质对于满足这些选择性要求至关重要。相对于氢化步骤，加氢甲酰化步骤的速率需要快速。胺在配位领域和水（大概在第二个领域）对机理的作用还需要进一步研究。类似地，胺的对映选择性合成尚不能直接实现，中断的工艺或使用不对称的有机催化的还原胺化反应是生产手性胺的有效合成方法。在许多情况下，已经证明了通过双相或（半）异质化系统将催化剂从有机产物中分离出来并进行再循环。
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