SN2'-Reactions of Peptide Aziridines. A Cuprate-Based Approach to (E)-Alkene Isosteres
SN2'-Reactions of Peptide Aziridines. A Cuprate-Based Approach to (E)-Alkene Isosteres
复制标题
DOI：
10.1021/jo00096a033
复制
发表时间：
1994-08
影响因子：
3.6
通讯作者：
P. Wipf;P. Fritch
中科院分区：
文献类型：
--
作者：
P. Wipf;P. Fritch
Alkenylaziridines were prepared from allylic alcohols via Sharpless epoxidation, oxirane to aziridine conversion under modified Staudinger conditions, and Wittig chain extension. Alternatively, β-hydroxy α-amino acids such as threonine can serve as readily available precursors. The corresponding N-acyl, -peptidyl-, -carbamoyl-, and -sulfonylaziridines underwent a high-yielding anti-S N 2' alkylation with organocopper/BF 3 complex to give (E)-alkene peptide isosteres in 62 to >98% de. The stereoselectivity of the addition process was studied by 1 H and 19 F NMR as well as chemical degradation. Alkene isosteres are important nonhydrolyzable and rigidified analogs of peptide bonds in biologically active peptides. This new methodology considerably facilitates the synthesis and the study of these peptide mimetics, since alkenylaziridines are readily prepared and side-chain modification is simplified by the wide range of functionalized organocopper reagents that are available
