3-NITRO-2-PYRIDINESULFENYL (NPYS) GROUP. A NOVEL SELECTIVE PROTECTING GROUP WHICH CAN BE ACTIVATED FOR PEPTIDE BOND FORMATION
3-NITRO-2-PYRIDINESULFENYL (NPYS) GROUP. A NOVEL SELECTIVE PROTECTING GROUP WHICH CAN BE ACTIVATED FOR PEPTIDE BOND FORMATION
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3-硝基-2-吡啶亚磺基 (NPYS) 基团。
DOI：
10.1002/chin.198111336
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发表时间：
1981
期刊：
影响因子：
--
通讯作者：
R. Walter
中科院分区：
文献类型：
--
作者：
R. Matsueda;R. Walter
报道了一种新型的3-硝基-2-吡啶磺基(Npys)，它对多肽合成中氨基和羟基的保护和活化具有重要作用。用3-硝基-2-吡啶磺酰氯处理氨基酸，很容易引入Npys基团。Npys基团很容易用非常稀的HCl处理，例如0.1-0.2N HCl在二氧六环中处理，但它对三氟乙酸和88%的甲酸有抵抗力。在中性条件下，用三苯基膦或2-吡啶硫醇-1-氧化物选择性地脱除N-吡啶，而不影响苄氧基(Z)、叔丁氧基(Boc)、2-(4-联苯基)丙基(2)氧基(BPOC)、9-荧甲氧基(Fmoc)、苯基(Bzl)或叔丁基(TBU)保护基团。然后-Npys Ando-Npys基团在RCOOH存在下通过氧化还原缩合添加叔膦形成的多肽或酯键而被激活。Npys基团的重要特征是通过在溶液中合成多肽和通过固相方法证明的，而不需要正式的去保护程序。在固相合成中，以4-(N-氧甲基)苯乙酸为关键中间体，将耐三氟乙酸的4-(氧甲基)苯乙酰胺连接基团引入到树脂中。
The novel 3‐nitro‐2‐pyridinesulfenyl (Npys) group, which is useful for the protection and the activation of amino and hydroxyl groups for peptide synthesis, is reported. The Npys group is readily introduced by treatment of amino acids with 3‐nitro‐2‐pyridinesulfenyl chloride. The Npys group is easily removed by treatment with very dilute HCl, e.g. 0.1‐0.2 N HCl in dioxane, but it is resistant to trifluoroacetic acid and 88% formic acid. Npys is also selectively removed under neutral conditions using triphenylphosphine or 2‐pyridinethiol 1‐oxide without affecting benzyloxycarbonyl (Z), tert‐butyloxycarbonyl (Boc), 2‐(4‐biphenylyl) propyl(2) oxycarbonyl (Bpoc), 9‐fluorenylmethyloxycarbonyl (Fmoc), benzyl (Bzl) ortert‐butyl(tBu) protecting groups. TheN‐Npys andO‐Npys groups when activated in the presence of RCOOH by the addition of tertiary phosphine form peptide or ester bonds via oxidation‐reduction condensation. The important features of the Npys group are demonstrated through the synthesis of peptides in solution and by solid phase methodology without a formal deprotection procedure. In solid phase synthesis, 4‐(Npys‐oxymethyl) phenylacetic acid is used as the key intermediate for the introduction of the trifluoroacetic acid resistant 4‐(oxymethyl) phenylacetamido linking group to the resin.