p-methoxybenzyl (E)-3-chloro-2-<2-oxo-3-(phenylacetamido)-4-<(phenylsulfonyl)thio>azetidin-1-yl>-4-<<(trifluoromethyl)sulfonyl>oxy>-2-butenoate | 168418-30-2

• 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: p-methoxybenzyl (E)-3-chloro-2-<2-oxo-3-(phenylacetamido)-4-<(phenylsulfonyl)thio>azetidin-1-yl>-4-<<(trifluoromethyl)sulfonyl>oxy>-2-butenoate
• 英文别名: (4-methoxyphenyl)methyl (E)-2-[(2R,3R)-2-(benzenesulfonylsulfanyl)-4-oxo-3-[(2-phenylacetyl)amino]azetidin-1-yl]-4-chloro-3-(trifluoromethylsulfonyloxy)but-2-enoate
• CAS: 168418-30-2
• 化学式: C₃₀H₂₆ClF₃N₂O₁₀S₃
• 分子量: 763.19
• InChiKey: GMINBYCCTBCORD-OKDHWRJWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  49
• 可旋转键数：
  15
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  205
• 氢给体数：
  1
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  p-methoxybenzyl (E)-3-chloro-2-<2-oxo-3-(phenylacetamido)-4-<(phenylsulfonyl)thio>azetidin-1-yl>-4-<<(trifluoromethyl)sulfonyl>oxy>-2-butenoate 在 1-甲基吡咯烷 、 N-甲基吡咯烷酮 、 三氯化铝 、 四氯化钛 、 氢化铝 、 lithium chloride 作用下， 以 二氯甲烷 为溶剂， 反应 10.5h， 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：

  三氟甲磺酸酐 、 (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 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以95%的产率得到p-methoxybenzyl (E)-3-chloro-2-<2-oxo-3-(phenylacetamido)-4-<(phenylsulfonyl)thio>azetidin-1-yl>-4-<<(trifluoromethyl)sulfonyl>oxy>-2-butenoate
  参考文献：
  名称：

  Synthesis of 2-exo-Methylenepenam by Reductive 1,2-Elimination and S–S Bond Fission in a PbBr₂/Al Bimetal System

  摘要：

  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。

  DOI：

  10.1246/cl.1995.709

文献信息

• Generation and reaction of copper(I) hydride in the copper(I) chloride–tributyltin hydride–NMP system: synthesis of 3-norcephalosporin
  作者：Hideo Tanaka、*Yoshihiko Yamaguchi、Shin-ichi Sumida、Manabu Kuroboshi、Misato Mochizuki、Sigeru Torii

  DOI：10.1039/a907049d

  日期：——

  Synthesis of 3-norcephalosporin 1 was performed successfully by reaction of either 3-trifluoromethylsulfonyloxy-Δ3-cephem 2, allenecarboxylate 3 or 3,4-disubstitued but-2-enoates 4 with copper(I) chloride and tributyltin hydride in N-methylpyrrolidin-2-one (NMP). Generation and reactions of a copper(I) hydride species in the copper(I) chloride–tributyltin hydride–NMP or N,N-dimethylformamide (DMF)

  通过任一的反应成功地进行3-三氟甲基- Δ3- norcephalosporin 1合成3 -cephem 2，allenecarboxylate 3或3,4-二取代丁-2- enoates 4铜（我）氯化物和三丁基锡氢化物在Ñ甲基吡咯-2-one（NMP）。代和铜（的反应我在铜）氢化物种（我），氯化三丁基锡氢化物的NMP或Ñ，ñ二甲基甲酰胺（DMF ）系统进行了讨论。
• 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。
• Synthesis of 3-Allyl- and 3-Benzyl-D3-cephems through Sequential Reductive 1,2-Elimination/Addition/Cyclization of 3,4-Disubstituted 2-Butenoates in Allyl and Benzyl Halides/Mn/NiCl2/AlCl3/NMP Systems
  作者：Hideo Tanaka、Yoshihisa Tokumaru、Sigeru Torii

  DOI：10.3987/com-99-s59

  日期：——

  One-pot synthesis of 3-allyl- and 3-benzyl-Delta(3)-cephems through a sequential reductive 1,2-elimination/addition/cyclization of 3, 4-disubstituted 2-[2-oxo-3-phenylacetamido-4-(phenylsulfonylthio)azetidin-1-yl]-2-butenoates was successfully performed by treatment with allyl and benzyl halides in an Mn/NiCl2(bpy)/AlCl3/N-methyl-2-pyrroridinone (NMP) system.
• 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.
• Synthesis of 2-<i>exo</i>-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
  作者：Hideo Tanaka、Shin-ichi Sumida、Yoichi Nishioka、Noriko Kobayashi、Yoshihisa Tokumaru、Yutaka Kameyama、Sigeru Torii

  DOI：10.1021/jo970051n

  日期：1997.5.1

  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.