Z(OMe)-Cys(Ad)-OH*DCHA | 103022-01-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Z(OMe)-Cys(Ad)-OH*DCHA
• 英文别名: Z(OMe)-Cys(Ad)-OH；(2R)-3-(1-adamantylsulfanyl)-2-[(4-methoxyphenyl)methoxycarbonylamino]propanoic acid
• CAS: 103022-01-1
• 化学式: C₂₂H₂₉NO₅S
• 分子量: 419.542
• InChiKey: NRTFSZRUXNLVKR-QPRVAFDKSA-N

物化性质

• 沸点：
  620.1±55.0 °C(Predicted)
• 密度：
  1.30±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.08
• 重原子数：
  29.0
• 可旋转键数：
  8.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  84.86
• 氢给体数：
  2.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  Z(OMe)-Cys(Ad)-OH*DCHA 在 三氟乙酸 作用下， 反应 60.0h， 生成 H-Cys(Ad)-OH
  参考文献：
  名称：

  Studies on peptides. CXXXIV. Evaluation of S-1-adamantylcysteine for peptide synthesis.

  摘要：

  与 S-对甲氧基苄基（MBzl）相比，半胱氨酸的 S-1-金刚烷基（Ad）对反式脂肪酸处理更稳定，但可在 60 分钟内被 0°C 三氟乙酸中的 1 M 三氟甲磺酸-硫代苯甲醚裂解，或在类似条件下被 (CF3COO)3 Tl 裂解。与 S-MBzl 基团相比，S-Ad-半胱氨酸不易形成亚砜。三甲基苯基硫代硅烷是一种有效的亚砜还原试剂。

  DOI：

  10.1248/cpb.34.869

文献信息

• Studies on peptides. CLII. Hard acid deprotecting procedure for peptide synthesis.
  作者：NOBUTAKA FUJII、AKIRA OTAKA、OSAMU IKEMURA、MIKA HATANO、AKIRA OKAMACHI、SUSUMU FUNAKOSHI、MITSUYA SAKURAI、TAKAYUKI SHIOIRI、HARUAKI YAJIMA

  DOI：10.1248/cpb.35.3447

  日期：——

  The use of trimethylsilyl trifluoromethanesulfonate as a peptide deprotecting reagent was examined, together with the role of soft bases employed. A new deprotecting procedure based on the hard acid principle is presented.

  考察了使用三甲基硅烷三氟甲磺酸酯作为肽脱保护试剂的效果，并探讨了软碱的作用。基于硬酸原理，提出了一种新的脱保护程序。
• Studies on peptides. CLI. Syntheses of cystine-peptides by oxidation of s-protected cysteine-peptides with thallium(III) trifluoroacetate.
  作者：NOBUTAKA FUJII、AKIRA OTAKA、SUSUMU FUNAKOSHI、KIYOSHI BESSHO、TOSHIHIRO WATANABE、KENICHI AKAJI、HARUAKI YAJIMA

  DOI：10.1248/cpb.35.2339

  日期：——

  Thallium (III) trifluoroacetate, a mild oxidant with a soft-acid character, was found to cleave various S-protecting groups of cysteine in trifluoroacetic acid, with spontaneous formation of cystine. Except for unmasked Trp and Met, other amino acids, including His and Tyr, remained intact in the presence of this oxidant. The usefulness of this oxidant for intramolecular disulfide bond-forming reactions was demonstrated by direct conversion of three model S-protected cysteine-peptides into cystine-peptides, i.e., oxytocin, urotensin II and human calcitonin generelated peptide.

  研究发现，三氟乙酸铊（III）是一种具有软酸性质的温和氧化剂，可裂解三氟乙酸中半胱氨酸的各种 S 保护基团，并自发形成胱氨酸。除了未屏蔽的 Trp 和 Met 外，包括 His 和 Tyr 在内的其他氨基酸在这种氧化剂的作用下保持完好无损。通过将三种受 S 保护的半胱氨酸肽模型（即催产素、尿促性素 II 和人类降钙素生成肽）直接转化为胱氨酸肽，证明了这种氧化剂在分子内二硫键形成反应中的作用。
• S-Benzyloxymethylcysteine, its properties and application in the synthesis of porcine brain natriuretic peptide (pBNP).
  作者：Akira OTAKA、Hiroshi MORIMOTO、Nobutaka FUJII、Takaki KOIDE、Susumu FUNAKOSHI、Haruaki YAJIMA

  DOI：10.1248/cpb.37.526

  日期：——

  The properties of S-benzyloxymethylcysteine, Cys(Bom), were examined. The S-Bom group is stable to trifluoroacetic acid (TFA), but is easily cleaved by treatment with silver trifluoromethanesulfonate (AgOTl)/TFA or 1 M trimethylsilyl trifluoromethanesulfonate (TMSOTf)-thioanisole/TFA. Cys(Bom) can be converted to cystine by treatment with thallium(III) trifluoroacetate.Cys(Bom)was successfully applied to the Fmoc-based solid phase synthesis of porcine brain natriuretic peptide (pBNP), a 26-residue peptide with one disulfide bond [Fmoc=9-fluorenylmethyloxycarbonyl]. In the final step, the peptide-resin was first treated with AgOTl/TFA, then with 1 M trimethyisllyl bromide-thioanisole/TFA. After dithiothreitol treatment and subsequent air-oxidation, a homogeneous pBNP was obtained in 17% yiled, based on the first amino acid loaded on the resin. The results was compared with those produced by other alternative deprotecting procedures.

  对S-苄氧基甲基半胱氨酸（Cys(Bom)）的性质进行了研究。S-Bom基团对三氟乙酸（TFA）稳定，但容易通过用三氟甲烷磺酸银（AgOTf）/TFA或1 M三甲基硅基三氟甲烷磺酸酯（TMSOTf）-硫代苯甲醚/TFA处理而被切除。Cys(Bom)可以通过处理氟化铊（III）三氟乙酸盐转化为半胱氨酸。Cys(Bom)成功应用于以Fmoc为基础的固相合成猪脑钠尿肽（pBNP），这是一种含有一个二硫键的26氨基酸肽[Fmoc=9-氟苯甲氧基羧基]。在最后一步中，肽-树脂首先用AgOTf/TFA处理，然后用1 M三甲基溴化硅-硫代苯甲醚/TFA处理。在二硫苏糖醇处理和随后的空气氧化后，得到了均一的pBNP，产率为17%，基于加载在树脂上的第一个氨基酸。将结果与其他替代去保护程序的结果进行了比较。
• Studies on peptides. CLVI. Synthesis of second human calcitonin gene-related peptide(.BETA.-hCGRP) by application of a new disulfide-bonding reaction with thallium(III) trifluoroacetate.
  作者：NOBUTAKA FUJII、TOSHIHIRO WATANABE、AKIRA OTAKA、KIYOSHI BESSHO、ITSUO YAMAMOTO、TOSHIHARU NODA、HARUAKI YAJIMA

  DOI：10.1248/cpb.35.4769

  日期：——

  A 37-residue peptide corresponding to the entire amino acid sequence of second human calcitonin gene-related peptide (β-hCGRP) was synthesized by assembling seven peptide fragments, followed by two successive treatments; i.e., first with thallium (III) trifluoroacetate to establish the disulfide bond between two Cys (Ad) residues and then with 1 M trimethylsilyl trifluoromethane-sulfonate/trifluoroacetic acid in the presence of diphenyl sulfide and ammonium iodide to remove all protecting groups employed and at the same time to reduce Met (O) to Met. The result was compared with that obtained by the usual air-oxidation procedure. Synthetic β-hCGRP exhibited a weak inhibitory action against bone Ca-resorption stimulated by [1-34] -parathyroid hormone in vitro and lowered the Ca and Pi levels in rat serum.

  通过将七个肽片段组合在一起，合成了与第二个人类降钙素基因相关肽（β-hCGRP）的整个氨基酸序列相对应的 37 个残基的肽，然后进行了两次连续处理，即先使用三氟乙酸铊（III）在两个 Cys（Ad）残基之间建立二硫键，然后使用 1 M 三甲基硅基三氟甲烷-磺酸盐/三氟乙酸铊（III）处理、先用三氟乙酸铊（III）在两个 Cys（Ad）残基之间建立二硫键，然后在二苯基硫醚和碘化铵存在下用 1 M 三甲基硅基三氟甲烷磺酸盐/三氟乙酸去除所有使用的保护基团，同时将 Met（O）还原为 Met。将结果与通常的空气氧化法进行比较。合成的 β-hCGRP 对体外[1-34] -甲状旁腺激素刺激的骨钙吸收有微弱的抑制作用，并能降低大鼠血清中 Ca 和 Pi 的水平。
• FUJII, NOBUTAKA;OTAKA, AKIRA;IKEMURA, OSAMU;HATANO, MIKA;OKAMACHI, AKIRA;+, CHEM. AND PHARM. BULL., 35,(1987) N 8, 3447-3452
  作者：FUJII, NOBUTAKA、OTAKA, AKIRA、IKEMURA, OSAMU、HATANO, MIKA、OKAMACHI, AKIRA、+

  DOI：——

  日期：——