p-methoxybenzyl 3-allyl-7-(phenylacetamido)-Δ³-cephem-4-carboxylate

• 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 3-allyl-7-(phenylacetamido)-Δ³-cephem-4-carboxylate
• 英文别名: p-Methoxybenzyl 3-allyl-7-phenylacetamido-Δ³-cephem-4-carboxylate；(4-methoxyphenyl)methyl (6R,7R)-8-oxo-7-[(2-phenylacetyl)amino]-3-prop-2-enyl-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate
• 化学式: C₂₆H₂₆N₂O₅S
• 分子量: 478.569
• InChiKey: FCUASHFFPXEODJ-RCZVLFRGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  34
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.27
• 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：

  三丁基乙烯基锡 、 7-苯乙酰氨基-3-氯甲基-4-头孢烷酸对甲氧基苄酯 在 tris-(dibenzylideneacetone)dipalladium(0) 、 三(2-呋喃基)膦 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以89%的产率得到p-methoxybenzyl 3-allyl-7-(phenylacetamido)-Δ³-cephem-4-carboxylate
  参考文献：
  名称：

  Palladium catalysis in cephalosporin chemistry: general methodology for the synthesis of cephem side chains

  摘要：

  DOI：

  10.1021/jo00310a014

文献信息

• A facile access to 3-allyl- and 3-benzyl-3-cephems via reductive addition/cylization of allenecarboxylate with allyl and benzyl halides in an Al/Pb/Ni redox system
  作者：Hideo Tanaka、Shin-ichi Sumida、Kouichi Sorajo、Sigeru Torii

  DOI：10.1039/c39940001461

  日期：——

  A sequential reductive addition/cyclization reaction of allenecarboyxlate, derived from penicillin G, with allyl and benzyl halides was successfully performed by the aid of aluminium metal ad catalytic amounts of PbBr2 and [NiCl2(bipy)] to afford 3-allyl- and 3-benzyl-3-cephems, respectively.

  成功地通过铝金属及催化量的PbBr2和[NiCl2(bipy)]，实现了从青霉素G衍生的丙二酸酯与烯丙和苄基卤化物的顺序还原加成/环化反应，分别得到3-烯丙基和3-苄基-3-头孢烯。
• Facile access to 3-allyl- and 3-benzyl-Δ3-cephems through reductive addition/cyclization of allenecarboxylate with allylic and benzylic halides in an [NiCl2(bipy)]/PbBr2/Al redox system
  作者：Hideo Tanaka、Shin-ichi Sumida、Kouichi Sorajo、Yutaka Kameyama、Sigeru Torii

  DOI：10.1039/a606049h

  日期：——

  Sequential reductive addition/cyclization of the allenecarboxylate 1, derived from penicillin G, with allylic and benzylic halides is successfully achieved by the aid of a three-metal redox system consisting of aluminium metal (2.5 molar equiv.) and catalytic amounts of [NiCl2(bipy)] (0.1 molar equiv.) and PbBr2 (0.05 molar equiv.) in N-methyl-2-pyrrolidone (NMP) to afford the corresponding 3-allyl- and 3-benzyl-Δ3-cephems 3a–i in 20–85% yields. The reactions of 1 with vinyl, prop-2-ynyl and phenyl halides in the same three-metal redox system result in the recovery of 1 and/or partial formation of 2-exo-methylenepenam 4. A similar electroreductive addition/cyclization of 1 with allyl bromide is performed by passage of an electrical current (3.2 F mol-1) in an [NiCl2(bipy)]/PbBr2/NMP/(Pt cathode)–(Al anode) system.

  顺序还原加成/环化反应成功地实现了来自青霉素G的烯丙基羧酸酯1与烯丙基和苄基卤化物的反应，该反应在由铝金属（2.5摩尔当量）和催化量的[NiCl2(bipy)]（0.1摩尔当量）以及PbBr2（0.05摩尔当量）组成的三金属氧化还原体系中进行，溶剂为N-甲基-2-吡咯烷酮（NMP），生成了相应的3-烯丙基和3-苄基Δ3-头孢菌素3a-i，产率为20-85%。在相同的三金属氧化还原体系中，1与乙烯基、丙-2-炔基和苯基卤化物的反应导致1的回收和/或部分生成2-外烯基青霉烯4。通过在[NiCl2(bipy)]/PbBr2/NMP/(铂阴极)–(铝阳极)体系中通电（3.2法拉/摩尔），对1进行类似的电还原加成/环化反应，反应物为烯丙溴。
• Synthesis of 3-Alkenyl-Δ³-cephems via Sequential Reductive 1,2-Elimination/Addition/Cyclization in an Alkenyltin/Copper(I) Chloride/bpy System
  作者：Hideo Tanaka、Yoshihisa Tokumaru、Sigeru Torii

  DOI：10.1055/s-1999-2735

  日期：1999.6

  A sequential reductive 1,2-elimination-addition-cyclization of 3,4-disubstituted butenoates derived from penicillin is performed successfully by treatment with alkenyltin, copper(I) chloride and 2,2′-bipyridine (bpy) in N-methyl-2-pyrrolidinone (NMP) to afford 3-alkenyl-Δ3-cephems.

  通过用链烯基锡、氯化亚铜和 2,2'-联吡啶 (bpy) 在 N-甲基- 溶液中处理，成功地对源自青霉素的 3,4-二取代丁烯酸酯进行连续还原 1,2-消除-加成-环化反应。 2-吡咯烷酮 (NMP) 提供 3-烯基-α3-头孢烯。
• 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.
• Synthesis of 3-Alkenyl- and 3-Arylalkyl-Δ³-cephems by Use of Terpyridine- or Bipyridine-Ligated Organocopper Species
  作者：Hideo Tanaka、Shin-ichi Sumida、Sigeru Torii

  DOI：10.1021/jo970041m

  日期：1997.5.1