(2R,3R,6R)-6-carboxymethyl-3-tert-butyldimethylsilyloxy-2-tert-butyldimethylsilyloxymethylpiperidine | 216860-78-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: (2R,3R,6R)-6-carboxymethyl-3-tert-butyldimethylsilyloxy-2-tert-butyldimethylsilyloxymethylpiperidine
• 英文别名: 2-[(2R,5R,6R)-5-[tert-butyl(dimethyl)silyl]oxy-6-[[tert-butyl(dimethyl)silyl]oxymethyl]piperidin-2-yl]acetic acid
• CAS: 216860-78-5
• 化学式: C₂₀H₄₃NO₄Si₂
• 分子量: 417.737
• InChiKey: WEMOYIZPJJOEEU-BRWVUGGUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.99
• 重原子数：
  27
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  67.8
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2R,3R,6R)-6-carboxymethyl-3-tert-butyldimethylsilyloxy-2-tert-butyldimethylsilyloxymethylpiperidine 在 N,N-二异丙基乙胺 、 2-氯-1-甲基吡啶鎓三氟甲烷磺酸盐 作用下， 以 乙腈 为溶剂， 反应 16.25h， 以90%的产率得到(2R,3R,6R)-8-oxo-3-tert-butyldimethylsilyloxy-2-tert-butyldimethylsilyloxymethyl-1-azabicyclo[4.2.0]octane
  参考文献：
  名称：

  Synthesis of Carbacephems from Serine

  摘要：

  Carbacephems have been synthesized from D-serine by two routes involving construction first of the six-membered ring followed by cyclization to give the bicyclic beta-lactam. In one route, alkylation of a lactim ether was accomplished with Ni(Acac)(2) as a catalyst. The desired R stereochemistry at the carbon corresponding to C-6 of the cephem was obtained by stereospecific hydrogenation of a vinylogous carbamate. The second route involved a stereospecific Michael cyclization to give the same C-6 stereochemistry. Closure of a piperidyl beta-amino acid intermediate common to both routes was accomplished using a modified Mukaiyama reagent found to be superior in our system to the traditional reagent. The resulting carbacephem core was stereospecifically substituted at C-7 with an ethyl or amino functionality. The ethylated intermediate was transformed into a stable enol triflate useful for the further elaboration of biologically important carbacephems.

  DOI：

  10.1021/jo980592s
• 作为产物：
  描述：

  (2R,3R)-6-oxo-3-tert-butyldimethylsilyloxy-2-(tert-butyldimethylsilyloxymethyl)piperidine 在 bis(acetylacetonate)nickel(II) 、 platinum on activated charcoal lithium hydroxide 、 氢气 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 氯仿 、 水 、 乙酸乙酯 为溶剂， 20.0 ℃ 、344.74 kPa 条件下， 反应 112.0h， 生成 (2R,3R,6R)-6-carboxymethyl-3-tert-butyldimethylsilyloxy-2-tert-butyldimethylsilyloxymethylpiperidine
  参考文献：
  名称：

  Synthesis of Carbacephems from Serine

  摘要：

  Carbacephems have been synthesized from D-serine by two routes involving construction first of the six-membered ring followed by cyclization to give the bicyclic beta-lactam. In one route, alkylation of a lactim ether was accomplished with Ni(Acac)(2) as a catalyst. The desired R stereochemistry at the carbon corresponding to C-6 of the cephem was obtained by stereospecific hydrogenation of a vinylogous carbamate. The second route involved a stereospecific Michael cyclization to give the same C-6 stereochemistry. Closure of a piperidyl beta-amino acid intermediate common to both routes was accomplished using a modified Mukaiyama reagent found to be superior in our system to the traditional reagent. The resulting carbacephem core was stereospecifically substituted at C-7 with an ethyl or amino functionality. The ethylated intermediate was transformed into a stable enol triflate useful for the further elaboration of biologically important carbacephems.

  DOI：

  10.1021/jo980592s

文献信息

• Synthesis of Carbacephems from Serine
  作者：James J. Folmer、Carles Acero、Dung L. Thai、Henry Rapoport

  DOI：10.1021/jo980592s

  日期：1998.11.1

  Carbacephems have been synthesized from D-serine by two routes involving construction first of the six-membered ring followed by cyclization to give the bicyclic beta-lactam. In one route, alkylation of a lactim ether was accomplished with Ni(Acac)(2) as a catalyst. The desired R stereochemistry at the carbon corresponding to C-6 of the cephem was obtained by stereospecific hydrogenation of a vinylogous carbamate. The second route involved a stereospecific Michael cyclization to give the same C-6 stereochemistry. Closure of a piperidyl beta-amino acid intermediate common to both routes was accomplished using a modified Mukaiyama reagent found to be superior in our system to the traditional reagent. The resulting carbacephem core was stereospecifically substituted at C-7 with an ethyl or amino functionality. The ethylated intermediate was transformed into a stable enol triflate useful for the further elaboration of biologically important carbacephems.