N-(benzyloxycarbonyl)-S-phenyl-L-cysteinyl-D-valine methyl ester | 123201-59-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: N-(benzyloxycarbonyl)-S-phenyl-L-cysteinyl-D-valine methyl ester
• 英文别名: Cbz-Cys(Ph)-D-Val-OMe；methyl (2R)-3-methyl-2-[[(2R)-2-(phenylmethoxycarbonylamino)-3-phenylsulfanylpropanoyl]amino]butanoate
• CAS: 123201-59-2
• 化学式: C₂₃H₂₈N₂O₅S
• 分子量: 444.552
• InChiKey: AFJSGGORVDQYPU-VQTJNVASSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  31
• 可旋转键数：
  12
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  119
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  N-(benzyloxycarbonyl)-S-phenyl-L-cysteinyl-D-valine methyl ester 在 sodium periodate 、 1-(叔丁基二甲基硅氧基)-2-丙酮 、 zinc(II) iodide 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 60.0h， 生成 methyl (2R)-2-[[(2R)-3-[tert-butyl(dimethyl)silyl]oxy-2-(phenylmethoxycarbonylamino)-3-phenylsulfanylpropanoyl]amino]-3-methylbutanoate
  参考文献：
  名称：

  Pummerer-type Cyclization of Arnstein Tripeptide Analogs Induced by O-Silylated Ketene Acetals: Studies of Penicillin Biosynthesis

  摘要：

  We report the first biomimetic conversion of Arnstein tripeptide analogues (1a and 1b) into cis beta-lactams (2a and 2b) using 0-silylated ketene acetal (3) involving asymmetric induction from the sulfoxide sulfur to the alpha-carbon. The peptide 1 was treated with 3 at room temperature in the presence of a catalytic amount of ZnI2 in MeCN to give cis-2, trans-2, and alpha-siloxysulfide (7). Reaction of R-1 with 3 gave cis-2 predominantly, and S-1 gave a mixture of cis-2 and trans-2. High cis selectivity was obtained by the use of a large volume of solvent and was strongly influenced by the absolute stereochemistry of the sulfoxide, the cysteinyl amino group, and the volume of solvent. The cis beta-lactams (2a,b) were obtained preferentially from R-1a,b. These chemical transformations strongly support Baldwin's mechanism which involves the initial formation of the cis beta-lactam by the Pummerer-type cyclization of the Arnstein tripeptide in penicillin biosynthesis and provide useful information on the first key step in penicillin biosynthesis.

  DOI：

  10.1021/ja00091a013
• 作为产物：
  描述：

  S-苯基-L-半胱氨酸 在 sodium hydroxide 、 (乙氧基乙炔基)(三甲基)硅烷 作用下， 生成 N-(benzyloxycarbonyl)-S-phenyl-L-cysteinyl-D-valine methyl ester
  参考文献：
  名称：

  O-甲硅烷基烯酮缩醛的化学：顺式-β-内酰胺的仿生合成

  摘要：

  描述了通过硅诱导的Pummerer型重排将Arnstein三肽类似物首次成功的仿生转化为顺式-β-内酰胺。

  DOI：

  10.1016/s0040-4039(01)80294-x

文献信息

• Chemistry of O -silylated ketene acetals: Biomimetic synthesis of cis -β-lactams
  作者：Yasuyuki Kita、Osamu Tamura、Takashi Miki、Hideyuki Tono、Norio Shibata、Yasumitsu Tamura

  DOI：10.1016/s0040-4039(01)80294-x

  日期：——

  The first successful biomimetic conversion of an Arnstein tripeptide analogue into the cis-β-lactam via a silicon-induced Pummerer-type rearrangement is described.

  描述了通过硅诱导的Pummerer型重排将Arnstein三肽类似物首次成功的仿生转化为顺式-β-内酰胺。
• KITA, YASUYUKI;TAMURA, OSAMU;MIKI, TAKASHI;TONO, HIDEYUKI;SHIBATA, NORIO;+, TETRAHEDRON LETT., 30,(1989) N, C. 729-730
  作者：KITA, YASUYUKI、TAMURA, OSAMU、MIKI, TAKASHI、TONO, HIDEYUKI、SHIBATA, NORIO、+

  DOI：——

  日期：——
• Pummerer-type Cyclization of Arnstein Tripeptide Analogs Induced by O-Silylated Ketene Acetals: Studies of Penicillin Biosynthesis
  作者：Yasuyuki Kita、Norio Shibata、Noriyuki Kawano、Takashi Tohjo、Chino Fujimori、Hirofumi Ohishi

  DOI：10.1021/ja00091a013

  日期：1994.6

  We report the first biomimetic conversion of Arnstein tripeptide analogues (1a and 1b) into cis beta-lactams (2a and 2b) using 0-silylated ketene acetal (3) involving asymmetric induction from the sulfoxide sulfur to the alpha-carbon. The peptide 1 was treated with 3 at room temperature in the presence of a catalytic amount of ZnI2 in MeCN to give cis-2, trans-2, and alpha-siloxysulfide (7). Reaction of R-1 with 3 gave cis-2 predominantly, and S-1 gave a mixture of cis-2 and trans-2. High cis selectivity was obtained by the use of a large volume of solvent and was strongly influenced by the absolute stereochemistry of the sulfoxide, the cysteinyl amino group, and the volume of solvent. The cis beta-lactams (2a,b) were obtained preferentially from R-1a,b. These chemical transformations strongly support Baldwin's mechanism which involves the initial formation of the cis beta-lactam by the Pummerer-type cyclization of the Arnstein tripeptide in penicillin biosynthesis and provide useful information on the first key step in penicillin biosynthesis.