Highly enantioselective thiourea-catalyzed nitro-Mannich reactions.
Highly enantioselective thiourea-catalyzed nitro-Mannich reactions.
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DOI：
10.1002/anie.200461814
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发表时间：
2005-01
影响因子：
--
通讯作者：
T. Yoon;E. Jacobsen
中科院分区：
文献类型：
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作者：
T. Yoon;E. Jacobsen
Mannich（或aza-Henry）反应是一种碳-碳键形成过程，可导致产生两个相邻的含氮立体中心。该反应允许直接进入各种含氮手性结构单元，例如通过还原硝基[1，2]的邻二胺和通过Nef反应的α-氨基羰基化合物。[3]因此，在过去的几年里，相当大的努力已经指向硝基-曼尼希反应的催化不对称版本的发展。Shibasaki等人描述了使用手性镱[4]和铝[5]催化剂将硝基烷烃对N-膦酰基亚胺的对映选择性加成，而Jørgensen埃塔尔描述了使用手性镱[4]和铝[5]催化剂将硝基烷烃对N-膦酰基亚胺对映选择性加成。已经报道了对α-亚氨基酯的不对称铜催化加成。[6]除了这些金属催化的变体，最近出现了两个对映选择性有机催化硝基曼尼希反应的报告。Takemoto等人已经报道了一种双官能硫脲催化剂，其在硝基甲烷与各种芳族N-膦酰基亚胺的加成中诱导适度的对映选择性，[7]和约翰斯顿等人已经开发了一种手性双脒三氟甲磺酸盐，其实现硝基乙烷与一系列缺电子N-Boc亚胺的非对映选择性加成。[八]《中国日报》
Mannich (or aza-Henry) reaction, is a carbon–carbon bondforming process that can result in the generation of two contiguous nitrogen-bearing stereogenic centers. This reaction allows straightforward entry to a variety of nitrogencontaining chiral building blocks such as vicinal diamines by reduction of the nitro group [1, 2] and α-amino carbonyl compounds by means of the Nef reaction.[3] As a result, considerable effort has been directed toward the development of catalytic asymmetric versions of the nitro-Mannich reaction over the past several years. Shibasaki et al. have described the enantioselective addition of nitroalkanes to N-phosphinoyl imines using chiral ytterbium [4] and aluminum [5] catalysts, while Jørgensen etal. have reported asymmetric coppercatalyzed additions to α-iminoesters.[6] Beyond these metal-catalyzed variants, two reports of enantioselective organocatalytic nitro-Mannich reactions have appeared recently. Takemoto et al. have reported a bifunctional thiourea catalyst that induces moderate enantioselectivity in the addition of nitromethane to a variety of aromatic N-phosphinoyl imines,[7] and Johnston et al. have developed a chiral bisamidine triflate salt that effects the diastereoselective addition of nitroethane to a range of electron-deficient N-Boc imines.[8]