Foldamer-Mediated Remote Stereocontrol: > 1,60 Asymmetric Induction
Foldamer-Mediated Remote Stereocontrol: > 1,60 Asymmetric Induction
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DOI：
10.1002/anie.201308264
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发表时间：
2014-01-03
影响因子：
16.6
通讯作者：
Clayden, Jonathan
中科院分区：
文献类型：
--
作者：
Byrne, Liam;Sola, Jordi;Clayden, Jonathan
N-末端L--甲基缬氨酸二聚体诱导对由非手性季氨基酸Aib和Ac（6）c形成的另外的非手性螺旋肽折叠体的螺旋义的完全构象控制。螺旋的持续右手螺旋感偏好使得远程反应位点能够受到末端手性残基的影响，并允许非对映选择性反应如烯烃氢化或亚胺离子加成发生1，16-、1，31-、1，46-甚至1，61-不对称诱导。立体化学信息可以以这种方式在高达4 nm的距离上进行通信。
An N-terminal L--methylvaline dimer induces complete conformational control over the screw sense of an otherwise achiral helical peptide foldamer formed from the achiral quaternary amino acids Aib and Ac(6)c. The persistent right-handed screw-sense preference of the helix enables remote reactive sites to fall under the influence of the terminal chiral residues, and permits diastereoselective reactions such as alkene hydrogenation or iminium ion addition to take place with 1,16-, 1,31-, 1,46- and even 1,61-asymmetric induction. Stereochemical information may be communicated in this way over distances of up to 4 nm.