methyl (2R)-3-methyl-2-[(3R,4S)-2-oxo-3-(phenylmethoxycarbonylamino)-4-phenylsulfanylazetidin-1-yl]butanoate | 123355-10-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酰胺类
• 英文名称: methyl (2R)-3-methyl-2-[(3R,4S)-2-oxo-3-(phenylmethoxycarbonylamino)-4-phenylsulfanylazetidin-1-yl]butanoate
• CAS: 123355-10-2
• 化学式: C₂₃H₂₆N₂O₅S
• 分子量: 442.536
• InChiKey: VGLBIAVPTSWLKC-SBHAEUEKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  31
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  110
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  N-Z-S-苯基-L-半胱氨酸 在 sodium periodate 、 1-羟基苯并三唑 、 1-(叔丁基二甲基硅氧基)-2-丙酮 、 三乙胺 、 N,N'-二环己基碳二亚胺 、 zinc(II) iodide 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 108.0h， 生成 methyl (2R)-3-methyl-2-[(3R,4S)-2-oxo-3-(phenylmethoxycarbonylamino)-4-phenylsulfanylazetidin-1-yl]butanoate
  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

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。
• 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.