The influence of fluoroalkyl-group electronegativity on stereocontrol in the synthesis of Ψ[CH(RF)NH]gly peptides

被引：13

作者：

Bigotti, Serena ^{[1
,2
]}

Volonterio, Alessandro ^{[1
,2
]}

Zanda, Matteo ^{[3
]}

机构：

[1] G Natta, Dipartimento Chim Mat & Ingn Chim, I-20131 Milan, Italy

[2] Politecn Milan, I-20131 Milan, Italy

[3] Ist Chim Riconoscimento Mol, CNR, Sez A Quil, I-20131 Milan, Italy

来源：

SYNLETT | 2008年 / 07期

关键词：

peptidomimetics; fluorine; electronegativity; peptide bond surrogate; fluoroalkyl;

D O I：

10.1055/s-2008-1072653

中图分类号：

O62 [有机化学];

学科分类号：

070303 [有机化学]; 081704 [应用化学];

摘要：

New peptidomimetics featuring CH(R(F))NH units, having different degree of fluorination, as peptide-bond surrogates have been synthesized. The key step in the synthesis consists of a stereoselective aza-Michael addition of chiral a-amino acid esters to beta-fluoroalkyl-alpha-nitroethenes. The diastereoselection of the process was influenced by the electronegativity, rather than by the steric bulk, of the fluorinated residue R(F) in beta-position of the nitroalkene acceptors. Replacement of a single F atom of R(F) by a hydrogen or methyl group brings about a dramatic drop of stereocontrol, whereas Br, Cl, and CF(3), albeit bulkier than F, provide poorer results in terms of stereocontrol.

引用

页码：958 / 962

页数：5

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