Catalytic enantioselective desymmetrization of meso-N-acylaziridines with TMSCN
Catalytic enantioselective desymmetrization of meso-N-acylaziridines with TMSCN
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DOI：
10.1021/ja053486y
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发表时间：
2005-08-17
影响因子：
15
通讯作者：
Shibasaki, M
中科院分区：
文献类型：
--
作者：
Mita, T;Fujimori, L;Shibasaki, M
以Gd（OiPr）3和d-葡萄糖衍生配体1为催化剂，研究了meso-N-对硝基苯甲酰基氮杂环丙烷与TMSCN的不对称催化反应.在该反应中，添加催化量的三氟乙酸（TFA）改善了对映选择性。在0 - 60 °C下，从一系列meso-氮杂环丙烷中获得了高的对映选择性。该产物易于转化为β-氨基酸。因此，所开发的催化对映选择性去对称化反应允许高效催化合成手性环状β-氨基酸。利用ESI-MS观察到TFA掺入到催化剂络合物中。这种新络合物的产生可能是改善对映选择性的起源。
A catalytic enantioselective desymmetrization ofmeso-N-p-nitrobenzoylaziridines with TMSCN was developed using a chiral gadolinium catalyst generated from Gd(OiPr)3andd-glucose-derived ligand1. In this reaction, the addition of a catalytic amount of trifluoroacetic acid (TFA) improved enantioselectivity. High enantioselectivity was obtained from a range ofmeso-aziridines at 0−60 °C. The product could be easily transformed into β-amino acids. Thus, the developed catalytic enantioselective desymmetrization reaction allowed for efficient catalytic synthesis of chiral cyclic β-amino acids. The incorporation of TFA into the catalyst complex was observed using ESI-MS. Generation of this new complex might be the origin of the improved enantioselectivity.