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Nitroxyl Peptides as Catalysts of enantioselective Oxidations

机译:硝基氧肽作为对映选择性氧化的催化剂

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摘要

The achiral, nitroxyl-containing #alpha#-amino acid TOAC (TOAC = 2,2,6,6-tetramethylpiperidine-1-oxyl-4-amino-4-carboxylic acid), in combination with the chiral #alpha#-amino acid C~(#alpha#-methyl valine [(#alpha#Me)Val], was used to prepare short peptides (from di- to hexa-) that induced the enantioselective oxidation of racemic 1-phenylethanol to 1-phenylethanol to acetophenone. The best catalyst was an N~#alpha#-acylated dipeptide alkylamide with the -TOAC-(#alpha#Me)Val- sequence folded in a stable, intramolecularly hydrogen-bonded #beta#-turn conformation with large, lipophilic (hydrophobic) N- and C-terminal blocking groups. We ration alized our findings by proposing models for the diastereomeric intermediates between (R)-[and (S)]-1-phenylethanol and the catalyst Fmoc-TOAC-L-(#alpha#Me)Val-NhiPr, based on the X-ray diffraction structure of the latter.
机译:与手性#alpha#-氨基结合使用的非手性,含硝基氧基的#alpha#-氨基酸TOAC(TOAC = 2,2,6,6-四甲基哌啶-1-氧基1-4-氨基-4-羧酸)酸C〜(#alpha#-甲基缬氨酸[(#alpha#Me)Val]用于制备短肽(从二到六价),该短肽可诱导外消旋的1-苯基乙醇对映体选择性氧化为1-苯基乙醇为苯乙酮最好的催化剂是N-#α#-酰化的二肽烷基酰胺,其-TOAC-(#alpha#Me)Val-序列折叠成稳定的,分子内氢键的#beta#-转构型,具有大的亲脂性(疏水性) N和C端封闭基团。我们提出了(R)-[和(S)]-1-苯基乙醇与催化剂Fmoc-TOAC-L-(#alpha# Me)Val-NhiPr,基于后者的X射线衍射结构。

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