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首页> 外文期刊>Chemistry: A European journal >alpha,alpha-Disubstituted Glycines Bearing a Large Hydrocarbon Ring:Peptide Self-Assembly through Hydrophobic Recognition
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alpha,alpha-Disubstituted Glycines Bearing a Large Hydrocarbon Ring:Peptide Self-Assembly through Hydrophobic Recognition

机译：带有大烃环的α，α-二取代甘氨酸：通过疏水识别作用的肽自组装

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摘要

A method was developed for synthesizing a,a-disubstituted glycine residues bearing a large(more than 15-membered)hydrophobia ring.The ring-closing metathesis reactions of the dialkenylated malonate precursors proceed efficiently,particularly when long methylene chains tether both terminal olefin groups.Surprisingly,the amino groups of these alpha,alpha-disubstituted gly-cines are inert to conventional protective reactions(e.g.,N-tert-butoxycar-bonyl(Boc)protection:Boc_2O/4-dime-thylaminopyridine(DM AP)/CH_2C1_2; W-benzyloxycarbonyl(Z)protection: Z-C1/DMAP/CH_2C1_2).Curtius rearrangement of the carboxylic acid func tionality of the malonate derivative after ring-closing metathesis leads to formation of an amine functionality and can be catalyzed by diphenylphos-phoryl azide.However,only the intermediate isocyanates can be isolated,even in the presence of alcohols such as benzyl alcohol.The isocyanates obtained by Curtius rearrangement in an aprotic solvent(benzene)were isolated in high yields and treated with 9-fluore-nylmethanol in a high-boiling-point sol vent(toluene)under reflux to give the 7V-9-fluorenylmethoxycarbonyl(Fmoc)-protected aminomalonate derivatives in high yield.These hydrophobic amino acids can be incorporated into a peptide by Fmoc solid-phase peptide synthesis and the acid fluoride activation method.The stability of the mono-meric ex-helical structure of a 17-amino-acid peptide was enhanced by replacement of two alanine residues with two hydrophobic amino acid residues bearing a cyclic 18-membered ring.The results of sedimentation equilibrium studies suggested that the peptide assembles into hexamers in the presence of 100 mM NaCl.
机译：开发了一种合成带有大（大于15元）疏水性环的a，a-二取代的甘氨酸残基的方法。二烯丙基化丙二酸酯前体的闭环易位反应有效进行，特别是当长亚甲基链束缚两个末端烯烃基团时令人惊讶地，这些α，α-二取代的甘氨酸的氨基对常规保护反应是惰性的（例如，N-叔丁氧基羰基（Boc）保护：Boc_2O / 4-二苯甲基-乙氨基吡啶（DM AP）/ CH_2C1_2闭环易位后丙二酸酯衍生物的羧酸官能度的克尔修斯重排导致胺官能团的形成，并且可以被二苯基膦酰基荧光团催化;然而，即使在苯甲醇等醇类存在下，也只能分离出中间体异氰酸酯。在高质子传递溶剂（苯）中通过Curtius重排获得的异氰酸酯被高度分离。并在回流下在高沸点溶剂（甲苯）中用9-氟-萘甲醇处理，以高收率得到7V-9-芴基甲氧基羰基（Fmoc）-保护的氨基丙二酸酯衍生物，这些疏水性氨基酸可掺入通过Fmoc固相肽合成和酸性氟化物活化法制备一种肽。通过用两个带有氨基酸的疏水性氨基酸残基取代两个丙氨酸残基来增强17个氨基酸的肽的单体前螺旋结构的稳定性沉降平衡研究的结果表明，该肽在100 mM NaCl存在下组装成六聚体。

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