Loukas Vassilios, Noula Caterina, Kokotos George
Laboratory of Organic Chemistry, Department of Chemistry, University of Athens, Panepistimiopolis, Athens 15771, Greece.
J Pept Sci. 2003 May;9(5):312-9. doi: 10.1002/psc.458.
The synthesis of enantiopure gamma-substituted gamma-amino acids with proteinogenic side chains, starting from the corresponding natural alpha-amino acids, was studied. N-Protected amino aldehydes containing various protective groups were prepared from the corresponding amino alcohols by oxidation with NaOCl in the presence of AcNH-TEMPO and directly reacted with methyl, benzyl and tert-butyl phosphoranylidene acetate to produce alpha,beta-unsaturated gamma-amino esters. Simultaneous hydrogenation of the double bond and removal of either the benzyl or benzyloxycarbonyl group led to N- or C-protected gamma-amino acids in high yield. The enantiomeric purity was studied by 1H NMR analysis of Mosher amides and chiral HPLC analysis.
研究了从相应的天然α-氨基酸出发，合成具有蛋白质ogenic侧链的对映体纯γ-取代γ-氨基酸的方法。通过在AcNH-TEMPO存在下用NaOCl氧化相应的氨基醇，制备了含有各种保护基团的N-保护氨基醛，并使其直接与甲基、苄基和叔丁基亚甲基膦酸酯反应，生成α,β-不饱和γ-氨基酯。双键的同时氢化以及苄基或苄氧羰基的去除，以高产率得到了N-或C-保护的γ-氨基酸。通过Mosher酰胺的1H NMR分析和手性HPLC分析研究了对映体纯度。
