(2R,3R,6R)-6-methoxycarbonylmethyl-3-tert-butyldimethylsilyloxy-2-(tert-butyldimethylsilyloxymethyl)piperidine | 216860-86-5

• 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-methoxycarbonylmethyl-3-tert-butyldimethylsilyloxy-2-(tert-butyldimethylsilyloxymethyl)piperidine
• 英文别名: methyl 2-[(2R,5R,6R)-5-[tert-butyl(dimethyl)silyl]oxy-6-[[tert-butyl(dimethyl)silyl]oxymethyl]piperidin-2-yl]acetate
• CAS: 216860-86-5
• 化学式: C₂₁H₄₅NO₄Si₂
• 分子量: 431.764
• InChiKey: PARGBRVDYWFPCV-KZNAEPCWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.08
• 重原子数：
  28
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  56.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2R,3R,6R)-6-methoxycarbonylmethyl-3-tert-butyldimethylsilyloxy-2-(tert-butyldimethylsilyloxymethyl)piperidine 在 ruthenium trichloride lithium hydroxide 、 sodium periodate 、 正丁基锂 、 对甲苯磺酸 、 二异丙胺 、 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 四氢呋喃 、 甲醇 、 四氯化碳 、 正己烷 、 水 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 100.25h， 生成 (2R,3R,6R,7R)-3-tert-butyldimethylsilyloxy-2-(p-nitrobenzyloxycarbonyl)-7-ethyl-8-oxo-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：

  (4R,5R)-4-Allyl-2,2-dimethyl-5-<(phenylsulfonyl)amino>-1,3-dioxane 在 吡啶 、 2,6-二甲基吡啶 、 盐酸 、 9-borabicyclo[3.3.1]nonane dimer 、 对羟基联苯 、 四乙基溴化铵 、 双(三甲基硅烷基)氨基钾 、 sodium hydride 、 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 甲醇 、 乙二醇二甲醚 、 二氯甲烷 、 甲苯 、 乙腈 为溶剂， 反应 215.75h， 生成 (2R,3R,6R)-6-methoxycarbonylmethyl-3-tert-butyldimethylsilyloxy-2-(tert-butyldimethylsilyloxymethyl)piperidine
  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