Construction of Vicinal Quaternary Stereogenic Centers by Enantioselective Direct Mannich-Type Reaction Using a Chiral Bis(guanidino)iminophosphorane Catalyst
Construction of Vicinal Quaternary Stereogenic Centers by Enantioselective Direct Mannich-Type Reaction Using a Chiral Bis(guanidino)iminophosphorane Catalyst
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DOI：
10.1002/anie.201601352
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发表时间：
2016-04-04
影响因子：
16.6
通讯作者：
Terada, Masahiro
中科院分区：
文献类型：
--
作者：
Takeda, Tadahiro;Kondoh, Azusa;Terada, Masahiro
开发了一种新型的不对称直接曼尼希型反应，该反应由-亚氨基苯乙酸酯与-位带有取代基的硫代内酯（作为酸性较低的亲核试剂）进行。使用双（胍基）亚氨基膦作为手性有机超强碱催化剂，该反应以良好的产率和高的非对映体和对映体选择性提供了具有邻位四元立体中心的密集官能化的氨基酸衍生物，其中之一是全碳四元立体中心。
A novel asymmetric direct Mannich-type reaction of -iminophenylacetate esters with thionolactones, bearing a substituent at the -position, as a less acidic pronucleophile was developed. Using bis(guanidino)iminophosphorane as the chiral organosuperbase catalyst, the reaction afforded densely functionalized amino-acid derivatives having vicinal quaternary stereogenic centers, one of which is an all-carbon quaternary stereogenic center, in good yield with high diastereo- and enantioselectivities.