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-吡啶硫基 (Npys) 基团。
DOI：
10.1111/j.1399-3011.1980.tb02963.x
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发表时间：
2009
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
报道了一种新的3-硝基-2-吡啶硫基（Npys），它可用于保护和活化肽合成中的氨基和羟基。通过用3-硝基-2-吡啶磺酰氯处理氨基酸，可以容易地引入Npys基团。Npys基团很容易通过用非常稀的HCl（例如0.1-0.2 N HCl的二氧六环溶液）处理而除去，但耐三氟乙酸和88%甲酸。在中性条件下使用三苯基膦或2-吡啶乙氧基1-氧化物也可选择性地除去Npys，而不影响苄氧基羰基（Z）、叔丁氧基羰基（Boc）、2-（4-联苯基）丙基（2）氧基羰基（Bpoc）、9-芴基甲氧基羰基（Fmoc）、苄基（Bzl）或叔丁基（tBu）保护基。N-Npys和O-Npys基团在RCOOH存在下通过加入叔膦活化时，通过氧化还原缩合形成肽键或酯键。Npys基团的重要特征通过在溶液中合成肽和通过固相方法而不需要正式的脱保护程序来证明。在固相合成中，4-（Npys-氧甲基）苯乙酸用作将耐三氟乙酸的4-（氧甲基）苯乙酰氨基连接基团引入树脂的关键中间体。
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 is 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) or tert-butyl (tBu) protecting groups. The N-Npys and O-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.