(4-methoxyphenyl)methyl (E)-2-[(2R,3R)-2-(benzenesulfonylsulfanyl)-4-oxo-3-[(2-phenylacetyl)amino]azetidin-1-yl]-4-chloro-3-hydroxybut-2-enoate | 131857-34-6

• 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: (4-methoxyphenyl)methyl (E)-2-[(2R,3R)-2-(benzenesulfonylsulfanyl)-4-oxo-3-[(2-phenylacetyl)amino]azetidin-1-yl]-4-chloro-3-hydroxybut-2-enoate
• CAS: 131857-34-6
• 化学式: C₂₉H₂₇ClN₂O₈S₂
• 分子量: 631.127
• InChiKey: VQVBNLCJDSPCIN-OKDHWRJWSA-N

物化性质

• 密度：
  1.49±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  42
• 可旋转键数：
  13
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  173
• 氢给体数：
  2
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  (4-methoxyphenyl)methyl (E)-2-[(2R,3R)-2-(benzenesulfonylsulfanyl)-4-oxo-3-[(2-phenylacetyl)amino]azetidin-1-yl]-4-chloro-3-hydroxybut-2-enoate 在 1-甲基吡咯烷 、 N-甲基吡咯烷酮 、 三氯化铝 、 四氯化钛 、 三乙胺 、 氢化铝 、 lithium chloride 作用下， 以 二氯甲烷 为溶剂， 反应 11.5h， 生成
  参考文献：
  名称：

  Synthesis of 2-exo-Methylenepenam and 3-Chloro-Δ³-cephem through a Sequential Reductive 1,2-Elimination/S−S Bond Fission or Chloride Ion-Addition/Cyclization of 3,4-Disubstituted 2-Butenoates in Metal Salt/Metal Combinations

  摘要：

  Synthesis of 2-exo-methylenepenam 1 through a sequential reductive 1,2-elimination/S-S bond fission/cyclization of 6 was performed by treatment with a PbBr2/Al (or a BiCl3/Al) combination in DMF, while that of 3-chloro-Delta(3)-cephem 2 through reductive 1,2-elimination/chloride ion-addition/cyclization was attained by use of an AlCl3/Al combination in N-methylpyrrolidone (NMP). The selective transformation of 6 to the allenecarboxylate 3 was also achieved by treatment with an AlBr3/Al combination in NMP. Cyclic voltammograms of 3,4-disubstituted 2-[2-oxo-3-(phenylacetamido)-4-[(phenylsulfonyl)thio]azetidin-1-yl]-2-butenoates (6) exhibit two irreversible reduction peaks responsible for reductive 1,2-elimination of the 3,4-disubstituted 2-butenoate moiety (at less negative potential) and for reductive S-S bond fission of the (phenylsulfonyl)thio moiety, suggesting that the reductive 1,2-elimination of 6 leading to allenecarboxylate 3 would occur prior to the reductive S-S bond cleavage.

  DOI：

  10.1021/jo970051n
• 作为产物：
  描述：

  1-<2-chloromethyl-1-(p-methoxybenzyloxycarbonyl)-2-propen-1-yl>-3-(phenylacetamido)-4-(phenylsulfonylthio)-2-azetidinone 在 ruthenium trichloride 、 copper(II) sulfate 、 过碘酸 作用下， 生成 (4-methoxyphenyl)methyl (E)-2-[(2R,3R)-2-(benzenesulfonylsulfanyl)-4-oxo-3-[(2-phenylacetyl)amino]azetidin-1-yl]-4-chloro-3-hydroxybut-2-enoate
  参考文献：
  名称：

  A Facile Access to 3-Hydroxycephems from Penicillin G through Bi/Sn or Ti/Sn Redox-Promoted Cyclization of 4-(Phenylsulfonylthio)azetidinones

  摘要：

  在含有吡啶的 DMF 中，通过与 BiCl4/Sn 或 TiCl4/Sn 双金属氧化还原偶的作用，成功地将青霉素 G 衍生的 1-(3-氯-2-羟基-1-对甲氧基苄氧羰基-1-丙烯基)-4-(苯磺酰硫基)氮杂环丁酮直接转化为 3-羟基头孢。

  DOI：

  10.1246/cl.1990.1867

文献信息

• Synthesis of 2-<i>exo</i>-Methylenepenam by Reductive 1,2-Elimination and S–S Bond Fission in a PbBr₂/Al Bimetal System
  作者：Hideo Tanaka、Youichi Nishioka、Yutaka Kameyama、Shin-ichi Sumida、Hiroyuki Matsuura、Sigeru Torii

  DOI：10.1246/cl.1995.709

  日期：1995.8

  A convenient synthesis of 2-exo-methylenepenam was performed by reductive elimination of a 3,4-disubstituted chlorine atom(s) and/or a triflate moiety and S-S bond fission of the phenylsulfonylthio group of p-methoxybenzyl 3,4-dichloro or 4-chloro-3-(trifluoromethylsulfonyloxy)-2-[4-(phenylsulfonylthio)-2-oxoazetidin-1-yl]-2-butenoate derived from penicillin G in a lead(II) bromide/aluminum bimetal redox system.

  通过还原消除 3,4-二取代的氯原子和/或三late 分子以及对甲氧基苄基 3-苯磺酰硫基的 S-S 键裂解，可以方便地合成 2-外-亚甲基环庚烷、4-二氯或 4-氯-3-(三氟甲基磺酰氧基)-2-[4-(苯磺酰硫基)-2-氧代氮杂环丁烷-1-基]-2-丁烯酸酯在溴化铅/铝双金属氧化还原体系中从青霉素 G 中衍生出来。
• TANAKA, HIDEO;TANIGUCHI, MASATOSHI;KAMEYAMA, YUTAKA;MONNIN, MARC;SASAOKA,+, CHEM. LETT.,(1990) N0, C. 1867-1868
  作者：TANAKA, HIDEO、TANIGUCHI, MASATOSHI、KAMEYAMA, YUTAKA、MONNIN, MARC、SASAOKA,+

  DOI：——

  日期：——
• Construction of cephem framework via sequential reductive 1,2-elimination–hydride addition in a tributyltin hydride–copper(<scp>I</scp>) chloride–NMP system: synthesis of 3-norcephalosporin
  作者：Hideo Tanaka、Yoshihiko Yamaguchi、Shin-ichi Sumida、Sigeru Torii

  DOI：10.1039/cc9960002705

  日期：——

  A sequential reductive 1,2-elimination and hydride addition process for 3,4-disubstituted butenoates derived from penicillin is successfully performed with the aid of a combination of tributyltin hydride and copper(I) chloride in N-methyl-2-pyrrolidinone (NMP) to afford 3-norcephalosporin.