allyl (4R,5S,6S)-3-benzylthio-6-[(1R)-1-(tert-butyldimethylsilyloxy)ethyl]-4-methyl-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate | 144837-72-9

• 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: allyl (4R,5S,6S)-3-benzylthio-6-[(1R)-1-(tert-butyldimethylsilyloxy)ethyl]-4-methyl-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate
• 英文别名: prop-2-enyl (4R,5S,6S)-3-benzylsulfanyl-6-[(1R)-1-[tert-butyl(dimethyl)silyl]oxyethyl]-4-methyl-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate
• CAS: 144837-72-9
• 化学式: C₂₆H₃₇NO₄SSi
• 分子量: 487.736
• InChiKey: DDKZHOJAPRMLTF-VURPSTOHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.75
• 重原子数：
  33
• 可旋转键数：
  11
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  81.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  allyl (4R,5S,6S)-3-benzylthio-6-[(1R)-1-(tert-butyldimethylsilyloxy)ethyl]-4-methyl-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate 在 氟化铵 、 氢氟酸 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 72.0h， 以96.5%的产率得到(4R,5S,6S)-3-Benzylsulfanyl-6-((R)-1-hydroxy-ethyl)-4-methyl-7-oxo-1-aza-bicyclo[3.2.0]hept-2-ene-2-carboxylic acid allyl ester
  参考文献：
  名称：

  Efficient synthesis of 1β-methylcarbapenems based on the counter-attack strategy

  摘要：

  A seven-step efficient synthesis of 1 beta-methylcarbapenems 1 from the acetoxyazetidinone 6 is described. The Reformatsky reaction of 3-(2-bromopropionyl)-1,3-benzoxazinone 7 with compound 6 gave an adduct 8 in 96% yield with high beta-selectivity (beta:alpha = 92:8). Compound 8 was transformed in three steps into the side-chain thiol esters 12a-e in good yields. The chlorotrimethylsilane-mediated Dieckmann-type cyclisation of thioesters 12b-e followed by counter-attack of the liberated thiolate anion 18 yielded the C-2 alkylthio- or arylthio-substituted 1 beta-methylcarbapenems 19b-e in a one-pot procedure. The synthesis of 1 beta-methylcarbapenems 1 was demonstrated by a simple cleavage of the silyl ether and allyl ester of compound 19b to afford target compound 1b in high yield.

  DOI：

  10.1039/p19960002851
• 作为产物：
  描述：

  (3S,4S)-1-(allyloxycarbonylmethyl)-3-[(1R)-1-(tert-butyldimethylsilyloxy)ethyl]-4-[(1R)-1-carboxyethyl]-2-azetidinone 在 四氯化钛 4-二甲氨基吡啶 、 三正丁胺 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 13.5h， 生成 allyl (4R,5S,6S)-3-benzylthio-6-[(1R)-1-(tert-butyldimethylsilyloxy)ethyl]-4-methyl-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate
  参考文献：
  名称：

  实用的新型脱水型Ti-Dieckmann缩合法合成1β-甲基卡巴南

  摘要：

  利用新型脱水类型的Ti-Dieckmann（分子内Ti-Claisen）缩合反应，可以高效，实用且立体控制地合成1β-甲基卡巴姆。与传统的碱性狄克曼缩合反应相比，该环化反应具有将硫醇部分直接掺入目标1β-甲基卡巴南的优点。另一个优点是使用对环境无害的（低毒性和安全的）试剂（TiCl 4和Et 3 N或Bu 3 N）。

  DOI：

  10.1002/adsc.200303065

文献信息

• Efficient synthesis of 1β-methylcarbapenems based on the counter-attack strategy
  作者：Masahiko Seki、Kazuhiko Kondo、Tameo Iwasaki

  DOI：10.1039/p19960002851

  日期：——

  A seven-step efficient synthesis of 1 beta-methylcarbapenems 1 from the acetoxyazetidinone 6 is described. The Reformatsky reaction of 3-(2-bromopropionyl)-1,3-benzoxazinone 7 with compound 6 gave an adduct 8 in 96% yield with high beta-selectivity (beta:alpha = 92:8). Compound 8 was transformed in three steps into the side-chain thiol esters 12a-e in good yields. The chlorotrimethylsilane-mediated Dieckmann-type cyclisation of thioesters 12b-e followed by counter-attack of the liberated thiolate anion 18 yielded the C-2 alkylthio- or arylthio-substituted 1 beta-methylcarbapenems 19b-e in a one-pot procedure. The synthesis of 1 beta-methylcarbapenems 1 was demonstrated by a simple cleavage of the silyl ether and allyl ester of compound 19b to afford target compound 1b in high yield.
• Practical Short Synthesis of 1β-Methylcarbapenem Utilizing a New Dehydration Type Ti-Dieckmann Condensation
  作者：Yoo Tanabe、Naoki Manta、Ryohei Nagase、Tomoniri Misaki、Yoshinori Nishii、Makoto Sunagawa、Akira Sasaki

  DOI：10.1002/adsc.200303065

  日期：2003.8

  An efficient, practical, and stereocontrolled synthesis of 1β-methylcarbapenems has been performed utilizing a new dehydration type of Ti-Dieckmann (intramolecular Ti-Claisen) condensation. This cyclization reaction has the advantage of direct incorporation of the thiol moiety into the target 1β-methylcarbapenem, compared with the traditional basic Dieckmann condensation. Another advantage is the use

  利用新型脱水类型的Ti-Dieckmann（分子内Ti-Claisen）缩合反应，可以高效，实用且立体控制地合成1β-甲基卡巴姆。与传统的碱性狄克曼缩合反应相比，该环化反应具有将硫醇部分直接掺入目标1β-甲基卡巴南的优点。另一个优点是使用对环境无害的（低毒性和安全的）试剂（TiCl 4和Et 3 N或Bu 3 N）。