3-methylene-7-oxo-6-phenylacetylamino-4-thia-1-aza-bicyclo[3.2.0]heptane-2-carboxylic acid 4-methoxybenzyl ester | 139371-98-5

• 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: 3-methylene-7-oxo-6-phenylacetylamino-4-thia-1-aza-bicyclo[3.2.0]heptane-2-carboxylic acid 4-methoxybenzyl ester
• 英文别名: (4-methoxyphenyl)methyl (2S,5R,6R)-3-methylidene-7-oxo-6-[(2-phenylacetyl)amino]-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate
• CAS: 139371-98-5
• 化学式: C₂₃H₂₂N₂O₅S
• 分子量: 438.504
• InChiKey: MLTJDPPNQLEBMP-KCZVDYSFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  31
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.26
• 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：

  (7R)-7-[(phenylacetyl)amino]-3-trifluoromethanesulfonyloxy-3-cephem-4-carboxylate, 4-methoxybenzyl ester 在 aluminum (III) chloride 、 bismuth(III) chloride 、 氢化铝 作用下， 以95%的产率得到3-methylene-7-oxo-6-phenylacetylamino-4-thia-1-aza-bicyclo[3.2.0]heptane-2-carboxylic acid 4-methoxybenzyl ester
  参考文献：
  名称：

  Process for producing exo-methylenepenam compounds

  摘要：

  本发明涉及一种制备外环亚甲基青霉烷化合物的方法，其中将头孢菌素化合物与具有标准氧化还原电位高达-0.3（V/SCE）的金属在摩尔比下至少一摩尔的量还原，并与具有比金属更高标准氧化还原电位的金属化合物在头孢菌素化合物的摩尔比下为0.001到10摩尔的量还原，其中X是卤素原子、低碳基磺酰氧基、三氟甲磺酰氧基、三氯甲磺酰氧基、芳基磺酰氧基、甲苯磺酰氧基或卤代磺酰氧基。

  公开号：

  US06339152B1

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。
• A convenient synthesis of 2-exo-methylene penam, a potent intermediate for new β-lactam antibiotics synthesis
  作者：Hideo Tanaka、Yutaka Kameyama、Atsuko Kosaka、Takahito Yamauchi、Sigeru Torii

  DOI：10.1016/0040-4039(91)80130-x

  日期：1991.12

  A convenient synthesis of 2-exo-methylene penams 1 was performed by transformation of thiazoline-azetidinones, derived from penicillin G, through intramolecular Michael addition. Manipulation of the exo-methylene moiety of 1 opened new entries to 2-oxopenam and 2β-thiomethyl substituted penams, respectively.

  通过分子内迈克尔加成，转化衍生自青霉素G的噻唑啉-氮杂环丁烷酮，可以方便地合成2-exo-亚甲基Penams 1。的外亚甲基部分的操作1打开了新的项，以分别2- oxopenam和2β硫代甲基取代的青霉烷。
• Conversion of Cephem into Penam/Penem through Sequential Ring-opening/Recyclization in an Al/BiCl₃/AlCl₃System
  作者：Hideo Tanaka、Yoshihisa Tokumaru、Yutaka Kameyama、Sigeru Torii

  DOI：10.1246/cl.1997.1221

  日期：1997.12

  A sequential reductive ring-opening/recyclization reaction of 3-substituted Δ3-cephems into 2-exo-methylenepenams and/or 2-methylpenems was successfully performed by treatment with Al/BiCl3/AlCl3 in NMP (N-methyl-2-pyrrolidinone). When the reaction was carried out in methanol, 3-norcephalosporin was formed as a major product.

  在 NMP（N-甲基-2-吡咯烷酮）中用 Al/BiCl3/AlCl3 处理 3-取代的 Δ3-cephem，成功地进行了将其转化为 2-外-亚甲基庚烷和/或 2-亚甲基庚烷的顺序还原开环/再环化反应。在甲醇中进行反应时，主要生成物为 3-去甲头孢菌素。
• 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。