| 139472-60-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酰胺类
• CAS: 139472-60-9
• 化学式: C₂₉H₂₆N₂O₇S₂
• 分子量: 578.667
• InChiKey: MBMIINHAZFBXKV-IXCJQBJRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  40
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  153
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  在 N-甲基吡咯烷酮 、 三正丁基氢锡 、 copper(l) chloride 作用下， 反应 1.0h， 以79%的产率得到3-Norcephalosporin
  参考文献：
  名称：

  氯化铜-氢化三丁基锡-NMP体系中氢化铜（I）的生成和反应：3-去头孢菌素的合成

  摘要：

  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。

  DOI：

  10.1039/a907049d
• 作为产物：
  描述：

  (4-methoxyphenyl)methyl (E)-2-[(2R,3R)-2-(benzenesulfonylsulfanyl)-4-oxo-3-[(2-phenylacetyl)amino]azetidin-1-yl]-4-chloro-3-(4-methylphenyl)sulfonyloxybut-2-enoate 在 锰 、 三氯化铝 、 二甲基氧化锡 作用下， 以 N-甲基吡咯烷酮 为溶剂， 反应 2.0h， 以80%的产率得到
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.3987/com-99-s59

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-Chloro-<i>Δ</i>³-cephem-4-carboxylate by Addition/Cyclization of Allenecarboxylate. Copper(II)-Promoted Aerobic Oxidation of Arenesulfinic Acids
  作者：Hideo Tanaka、Ryo Kikuchi、Sigeru Torii

  DOI：10.1246/bcsj.69.1391

  日期：1996.5

  The selective transformation of allenecarboxylate derived from penicillin into 3-chloro-Δ3-cephem-4-carboxylate was successfully achieved by an addition/cyclization reaction with chloride salts in aerobic media containing a copper(II) catalysts, in which copper(II)-catalyzed aerobic oxidation of in situ generated benzenesulfinate ion into less nucleophilic sulfonate ion prior to the nucleophilic addition

  通过在含有铜（II）催化剂的需氧介质中与氯化物盐的加成/环化反应，成功地实现了源自青霉素的丙二烯羧酸盐向 3-氯-Δ3-cephem-4-羧酸盐的选择性转化，其中铜（II）-在原位生成的苯亚磺酸根离子亲核加成到丙二烯羧酸根之前，催化有氧氧化原位生成的苯亚磺酸根离子为亲核性较低的磺酸根离子，这将完全消除不需要的 3-苯基磺酰基-Δ3-头孢烯-4-羧酸根的形成。在类似的有氧条件下，芳烃亚磺酸盐和芳烃亚磺酸分别被顺利氧化成相应的磺酸盐和磺酸。
• 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。
• A facile synthesis of C(3)-alkenyl substituted cephems through addition-cyclization of allenecarboxylates derived from penicillin
  作者：Hideo Tanaka、Yutaka Kameyama、Shin-ichi Sumida、Sigeru Torii

  DOI：10.1016/s0040-4039(00)60924-3

  日期：1992.11

  A short-cut route to cephalosporins bearing alkenyl substituents on the C(3)-position through copper(I) chloride-promoted Michael-type addition of alkenyltributyltins to allenecarboxylates, derived from penicillin, is described.

  描述了一条通向头孢菌素的捷径，该头孢菌素通过氯化铜（I）促进烯基三丁基锡与烯丙基羧酸酯的迈克尔型加成反应而衍生自青霉素，而头孢菌素在C（3）-位上带有烯基取代基。