4-Nitrobenzyl (1R,5S,6S)-6-[1(R)-t-butyldimethylsilyloxyethyl]-2-ethylthio-1-methyl-1-carbapen-2-em-3-carboxylate | 158168-56-0

• 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: 4-Nitrobenzyl (1R,5S,6S)-6-[1(R)-t-butyldimethylsilyloxyethyl]-2-ethylthio-1-methyl-1-carbapen-2-em-3-carboxylate
• 英文别名: (4-nitrophenyl)methyl (4R,5S,6S)-6-[(1R)-1-[tert-butyl(dimethyl)silyl]oxyethyl]-3-ethylsulfanyl-4-methyl-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate
• CAS: 158168-56-0
• 化学式: C₂₅H₃₆N₂O₆SSi
• 分子量: 520.722
• InChiKey: XVHQBRLMSOBACN-XNFNUYLZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.49
• 重原子数：
  35
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  127
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  4-Nitrobenzyl (1R,5S,6S)-6-[1(R)-t-butyldimethylsilyloxyethyl]-2-ethylthio-1-methyl-1-carbapen-2-em-3-carboxylate 在 palladium diacetate 1,1,2,3-四甲基胍 、 碳酸氢钠 、 间氯过氧苯甲酸 、 亚磷酸三乙酯 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 3.5h， 生成 (4-nitrophenyl)methyl (4S,5R,6S)-6-[(1R)-1-[tert-butyl(dimethyl)silyl]oxyethyl]-3-[[9-(2-hydroxyethyl)-2,2-dioxo-2lambda6-thia-3-azatricyclo[6.3.1.04,12]dodeca-1(12),4,6,8,10-pentaen-3-yl]methyl]-4-methyl-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate
  参考文献：
  名称：

  Sequential Nitromethane Conjugate Addition/Elimination−Pd-Catalyzed Allylation of β-Trifloxy Acrylates. Application to Carbapenem Synthesis

  摘要：

  [GRAPHICS]Sequential reactions of nitromethane via conjugate addition-elimination to beta-trifloxy acrylates followed by Pd-catalyzed substitution of the resulting allyl nitro compounds with nucleophiles afforded homologation products at the beta-position. 2-Naphthosultammethyl carbapenem, an anti-MRS carbapenem intermediate, was prepared in one pot from the corresponding 2-trifloxy compound. The scope and limitation of the one-pot method were investigated using several cyclic unsaturated esters and nucleophiles.

  DOI：

  10.1021/ol990299u
• 作为产物：
  描述：

  乙硫醇 、 (4R,5R,6S)-4-nitrobenzyl-6-((R)-1-((tert-butyldimethylsilyl)oxy)ethyl)-4-methyl-7-oxo-3-(((trifluoromethyl)sulfonyl)oxy)-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate 在 N,N-二异丙基乙胺 作用下， 以 乙腈 为溶剂， 以75%的产率得到4-Nitrobenzyl (1R,5S,6S)-6-[1(R)-t-butyldimethylsilyloxyethyl]-2-ethylthio-1-methyl-1-carbapen-2-em-3-carboxylate
  参考文献：
  名称：

  Sequential Nitromethane Conjugate Addition/Elimination−Pd-Catalyzed Allylation of β-Trifloxy Acrylates. Application to Carbapenem Synthesis

  摘要：

  [GRAPHICS]Sequential reactions of nitromethane via conjugate addition-elimination to beta-trifloxy acrylates followed by Pd-catalyzed substitution of the resulting allyl nitro compounds with nucleophiles afforded homologation products at the beta-position. 2-Naphthosultammethyl carbapenem, an anti-MRS carbapenem intermediate, was prepared in one pot from the corresponding 2-trifloxy compound. The scope and limitation of the one-pot method were investigated using several cyclic unsaturated esters and nucleophiles.

  DOI：

  10.1021/ol990299u

文献信息

• Azetidinone compounds useful in the preparation of carbapenem
  申请人：Sankyo Company, Limited

  公开号：US05541317A1

  公开（公告）日：1996-07-30

  Compounds of formula (I): ##STR1## wherein: R.sup.1 is hydrogen or a hydroxy-protecting group; R.sup.2 is alkyl, alkoxy, halogen, optionally substituted phenyl or optionally substituted phenoxy; R.sup.3 is optionally substituted pyridyl, optionally substituted quinolyl or phenyl group which has a substituent of formula --CYNR.sup.5 R.sup.6, where Y is oxygen or sulfur, and R.sup.5 and R.sup.6 are each alkyl, aryl or aralkyl, or R.sup.5 and R.sup.6 and the nitrogen to which they are attached together form a heterocyclic group; is R.sup.4 hydrogen or an amino-protecting group; and Z is sulfur or oxygen; are valuable intermediates in the preparation of carbapenem compounds and retain a desirable configuration during conversion to such carbapenem compounds. Penem and carbapenem compounds having a group of formula --SA' are prepared from a corresponding compound having a substituted thio, sulfinyl or sulfonyl group at this position by reaction with a compound A'SH (where A' is an organic group) in the presence of a salt of a metal of Group II or III of the Periodic Table.

  化合物的式子(I)：##STR1## 其中：R.sup.1为氢或羟基保护基；R.sup.2为烷基，烷氧基，卤素，可选择取代的苯基或可选择取代的苯氧基；R.sup.3为可选择取代的吡啶基，可选择取代的喹啉基或具有式子--CYNR.sup.5 R.sup.6的取代基的苯基，其中Y为氧或硫，而R.sup.5和R.sup.6均为烷基，芳基或芳基烷基，或R.sup.5和R.sup.6以及它们所连接的氮共同形成一个杂环基团；R.sup.4为氢或氨基保护基；Z为硫或氧；是制备碳青霉烯化合物的有价值的中间体，并在转化为碳青霉烯化合物期间保持理想的构型。具有式子--SA'的青霉烯和碳青霉烯化合物是通过与具有该位置的取代硫，亚砜或磺酰基的相应化合物在周期表第二或第三组金属的盐存在下与化合物A'SH（其中A'是有机基团）反应制备的。
• Silyl enol ether alkylation process
  申请人：Sankyo Company, Limited

  公开号：US05719275A1

  公开（公告）日：1998-02-17

  A method for preparing compounds of formula (I): ##STR1## wherein: R.sup.1 is hydrogen or a hydroxy-protecting group; R.sup.2 is alkyl, alkoxy, halogen, optionally substituted phenyl or optionally substituted phenoxy; R.sup.3 is optionally substituted pyridyl, optionally substituted quinolyl or phenyl group which has a substituent of formula --CYNR.sup.5 R.sup.6, where Y is oxygen or sulfur, and R.sup.5 and R.sup.6 are each alkyl, aryl or aralkyl, or R.sup.5 and R.sup.6 and the nitrogen to which they are attached together form a heterocyclic group; R.sup.4 is hydrogen or an amino-protecting group; and Z is sulfur or oxygen. The process comprises reacting a compound of formula (II): ##STR2## in which R.sup.8, R.sup.9 and R.sup.10 are the same or different and each represents an alkyl group having from 1 to 4 carbon atoms or a phenyl group, with a compound of formula (III): ##STR3## in which R.sup.11 represents an acyloxy, alkylsulfonyl, arylsulfonyl, alkylsulfinyl or arylsulfinyl group.

  一种制备式（I）化合物的方法：其中：R.sup.1是氢或羟基保护基；R.sup.2是烷基，烷氧基，卤素，可选地取代的苯基或可选地取代的苯氧基；R.sup.3是可选地取代的吡啶基，可选地取代的喹啉基或具有式--CYNR.sup.5 R.sup.6的取代基的苯基，其中Y是氧或硫，R.sup.5和R.sup.6分别是烷基，芳基或芳烷基，或R.sup.5和R.sup.6和它们所连接的氮共同形成一个杂环基；R.sup.4是氢或氨基保护基；Z是硫或氧。该过程包括将式（II）的化合物与式（III）的化合物反应：其中R.sup.8，R.sup.9和R.sup.10相同或不同，每个代表具有1至4个碳原子的烷基或苯基。其中，式（II）为：##STR2##式（III）为：##STR3##