College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China.
J Am Chem Soc. 2011 Aug 3;133(30):11757-65. doi: 10.1021/ja2043563. Epub 2011 Jul 13.
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.
一种新型的手性铜（I）/TF-BiphamPhos 配合物催化的亚胺叶立德与β-取代亚甲基双膦酸盐的不对称迈克尔加成反应得以实现。本体系为手性膦配体铜（I）催化的不对称迈克尔加成反应提供了一种独特而简便的方法，以高收率、优异的非对映选择性和对映选择性得到了含有手性 gem-双膦酸酯（gem-BPs）的非天然α-氨基酸衍生物。随后的转化可以在不损失非对映体过量和对映体过量的情况下，方便地制备含有 BP 和双膦酸酯的生物活性非天然α-氨基酸衍生物。
