A facile Cu(I)/TF-BiphamPhos-catalyzed asymmetric approach to unnatural α-amino acid derivatives containing gem-bisphosphonates.
A facile Cu(I)/TF-BiphamPhos-catalyzed asymmetric approach to unnatural α-amino acid derivatives containing gem-bisphosphonates.
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DOI：
10.1021/ja2043563
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发表时间：
2011-07
影响因子：
15
通讯作者：
Zhi-Yong Xue;Qing‐Hua Li;H. Tao;Chun‐Jiang Wang
中科院分区：
文献类型：
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作者：
Zhi-Yong Xue;Qing‐Hua Li;H. Tao;Chun‐Jiang Wang
在手性铜（I）/TF-BiphamPhos配合物存在下，实现了偶氮甲碱叶立德与β-取代亚烷基二磷酸酯的不对称Michael加成反应.本系统提供了一个独特的和方便的获得对映体富集的非天然α-氨基酸衍生物含有偕-双膦酸酯（gem-BP），在高产量与优秀的非对映体选择性和对映体选择性。随后的转化导致含有BP和双膦酸的生物活性非天然α-氨基酸衍生物的有利制备，而不损失非对映异构体和对映异构体过量。
A novel catalytic asymmetric Michael addition of azomethine ylide with β-substituted alkylidene bisphosphates was realized in the presence of a chiral copper(I)/TF-BiphamPhos complex. The present system provides a unique and facile access to enantioenriched unnatural α-amino acid derivatives containing gem-bisphosphonates (gem-BPs) in high yields with excellent diastereoselectivities and enantioselectivities. Subsequent transformations lead to the expedient preparation of biologically active unnatural α-amino acid derivatives containing BPs and bisphosphonic acids without loss of diastereo- and enantiomeric excess.