diphenylmethyl 7β-phenylacetamido-3-acetoxymethyl-3-cephem-4-carboxylate | 41128-81-8

• 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: diphenylmethyl 7β-phenylacetamido-3-acetoxymethyl-3-cephem-4-carboxylate
• 英文别名: (6R,7R)-benzhydryl 3-(acetyloxymethyl)-8-oxo-7-(2-phenylacetamido)-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate；(6R)-3-acetoxymethyl-8-oxo-7t-(2-phenyl-acetylamino)-(6rH)-5-thia-1-aza-bicyclo[4.2.0]oct-2-ene-2-carboxylic acid benzhydryl ester；7β-(2-phenyl-acetylamino)-cephalosporanic acid benzhydryl ester；benzhydryl (6R,7R)-3-(acetyloxymethyl)-8-oxo-7-[(2-phenylacetyl)amino]-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate
• CAS: 41128-81-8
• 化学式: C₃₁H₂₈N₂O₆S
• 分子量: 556.639
• InChiKey: SILHQPLECKIJRE-PDDLMNHVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  40
• 可旋转键数：
  11
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  127
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  diphenylmethyl 7β-phenylacetamido-3-acetoxymethyl-3-cephem-4-carboxylate 在 Candida antarctica lipase B 作用下， 以 四氢呋喃 、 正己烷 、 仲丁醇 为溶剂， 反应 96.0h， 以52%的产率得到diphenylmethyl 7β-phenylacetamido-3-hydroxymethyl-3-cephem-4-carboxylate
  参考文献：
  名称：

  Enzymatic Deprotection of the Cephalosporin 3′-Acetoxy Group Using Candida antarctica Lipase B

  摘要：

  Cephalosporins remain one of the most important classes of antibiotics. A useful site for derivatization involves generation of and chemistry at the 3'-hydroxymethyl position. While 3'-acetoxymethyl-substituted cephalosporins are readily available, deacetylation to access the free 3'-hydroxymethyl group is problematic when the carboxylic acid is protected as an ester. Herein we report that this important transformation has been efficiently accomplished using Candida antarctica lipase B. Although this transformation is difficult to carry out using chemical methods, the enzymatic deacetylation has been successful on gram scale, when the cephalosporin is protected as either the benzhydryl or tert-butyl esters and on the corresponding sulfoxide and sulfone of the tert-butyl ester.

  DOI：

  10.1021/jo902406b
• 作为产物：
  描述：

  二苯甲醇 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 diphenylmethyl 7β-phenylacetamido-3-acetoxymethyl-3-cephem-4-carboxylate
  参考文献：
  名称：

  7-氨基头孢酸合成 7α-甲氧基-7-（4-苯基-1H-1,2,3-三唑-1-基）乙酰氨基-3′-芳硫代-头孢菌酸衍生物

  摘要：

  该项目的目的是开发一种制备头霉素支架的合成方案，该方案将很容易合成其类似物，并在 C-7 氨基和 C-3′ 位置发生变化。我们还旨在开发一种避免使用有毒和潜在爆炸性二苯基重氮甲烷的方法。这些目标是通过合成新型 α-溴乙酰胺 18 来实现的，该 18 允许叠氮化物在 α-溴乙酰胺位置进行官能化，然后通过 Cu（I） 催化的叠氮化物-炔烃环加成反应引入 4-苯基-1H-1,2,3-三唑-1-基部分与苯乙炔反应。钯催化的芳硫代化反应随后允许引入 3′-芳基硫醇取代基。我们还首次报道了 （6R，7S）-3-[（乙酰氧基）甲基]-7-氨基-7-甲氧基-8-氧代-5-硫代-1-氮杂双环[4.2.0]辛-2-烯-2-羧酸的 4-甲氧基苄酯的合成，以及使用三氯乙酰胺二苯酯代替二苯基重氮甲烷和 4-甲氧基苄基三氯乙酰胺酯制备相关的 4-甲氧基苄酯。所描述的化学性质以及此处报道的几种合成中间体分别是进一步开发

  DOI：

  10.3390/molecules28217338

文献信息

• Reactions of TMSI with cephalosporin esters
  作者：Rosanne Bonjouklian、Michael L. Phillips

  DOI：10.1016/s0040-4039(01)82025-6

  日期：1981.1

  The direct synthesis of 3-iodomethyl cephalosporin esters from 3-acetoxy- and 3-carbamoylmethyl analogues may be achieved using TMSI. The “one-pot” conversion of sodium cephalothin into a C-3 heterocycle-substituted cephalosporin may also be performed using TMSI-mediated chemistry.

  使用TMSI可以从3-乙酰氧基-和3-氨基甲酰基甲基类似物直接合成3-碘甲基头孢菌素酯。也可以使用TMSI介导的化学方法将头孢菌素钠“一锅”转化为C-3杂环取代的头孢菌素。
• Synthesis of 3-Alkylidenecepham-4-carboxylic Acid derivatives by Samarium(II) Iodide Reduction
  作者：Han-Young Kang、Yong Seo Cho、Hun Yeong Koh、Moon Ho Chang

  DOI：10.1080/00397919308011140

  日期：1993.12

  Abstract Samarium(II) iodide promoted reductive deacetoxylation of 7-aminocephalosporanic acid derivatives to synthesize 3-alkylidenecepham-4-carboxylates, which could be valuable intermediates for the synthesis of new cephalosporin antibiotics, was investigated.

  摘要 研究了碘化钐 (II) 促进 7-氨基头孢烷酸衍生物的还原性脱乙酰氧基化反应合成 3-亚烷基萘普姆-4-羧酸盐，该化合物可能是合成新型头孢菌素抗生素的重要中间体。
• Deprotection of carboxylic esters of .beta.-lactam homologs. Cleavage of p-methoxybenzyl, diphenylmethyl, and tert-butyl esters effected by a phenolic matrix
  作者：Sigeru Torii、Hideo Tanaka、Masatoshi Taniguchi、Yutaka Kameyama、Michio Sasaoka、Takashi Shiroi、Ryo Kikuchi、Ichiro Kawahara、Akihiro Shimabayashi、Shigemitsu Nagao

  DOI：10.1021/jo00011a034

  日期：1991.5

  p-Methoxybenzyl, diphenylmethyl, and tert-butyl esters were deprotected by gentle heating in phenol. This method of ester cleavage played an important role in beta-lactam synthesis. The mechanism of the reaction is believed to involve a proton relay through a hydrogen-bonded phenolic matrix.
• A facile synthesis of 7-amino-3-desacetoxycephalosporanic acid derivatives by indium-mediated reduction of 3-iodomethylcephems in aqueous media
  作者：Hyungsun Chae、Sangwon Cho、Gyochang Keum、Soon Bang Kang、Ae Nim Pae、Youseung Kim

  DOI：10.1016/s0040-4039(00)00512-8

  日期：2000.5

  An efficient reductive conversion of 3-iodomethylcephalosporin and 3-acetoxymethylcephalosporin derivatives mediated by indium into the corresponding 3-methylcephems and 3-methylenecephams in moderate to good yields has been developed in an aqueous system. 3-Methylenecephams are converted into the corresponding 3-methylcephems under previously reported basic conditions quantitatively. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Pattenden, Gerald; Stapleton, Alan; Humber, David C., Journal of the Chemical Society. Perkin transactions I, 1988, p. 1685 - 1688
  作者：Pattenden, Gerald、Stapleton, Alan、Humber, David C.、Roberts, Stanley M.

  DOI：——

  日期：——