(2R,4R,5R)-2-benzyl-4-(methoxycarbonylmethyl)-1-(p-toluenesulfonyl)-5-[1-{(triethyl)silyl}vinyl]piperidine | 1254356-27-8

• 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,4R,5R)-2-benzyl-4-(methoxycarbonylmethyl)-1-(p-toluenesulfonyl)-5-[1-{(triethyl)silyl}vinyl]piperidine
• 英文别名: methyl 2-[(2R,4R,5R)-2-benzyl-1-(4-methylphenyl)sulfonyl-5-(1-triethylsilylethenyl)piperidin-4-yl]acetate
• CAS: 1254356-27-8
• 化学式: C₃₀H₄₃NO₄SSi
• 分子量: 541.827
• InChiKey: MXASYYUOEJVDQL-IUAQSZDVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  37
• 可旋转键数：
  12
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  72.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  (E)-4-acetoxy-3-(triethylsilyl)but-2-en-1-ol 在 四氯化碳 、 偶氮二异丁腈 、 四溴化碳 、 三正丁基氢锡 、 二异丁基氢化铝 、 caesium carbonate 、 三苯基膦 作用下， 以 二氯甲烷 、 甲苯 、 乙腈 为溶剂， 反应 47.08h， 生成 (2R,4R,5R)-2-benzyl-4-(methoxycarbonylmethyl)-1-(p-toluenesulfonyl)-5-[1-{(triethyl)silyl}vinyl]piperidine 、 (3R,4aR,5S,7S,7aR)-3-benzyl-5-methoxycarbonyl-1-(ptoluenesulfonyl)-7-[(triethyl)silyl]octahydro-1H-[2]pyrindene
  参考文献：
  名称：

  Stereoselective Synthesis of 2,4,5-Trisubstituted Piperidines via Radical Cyclization

  摘要：

  A novel approach to 2,4,5-trisubstituted piperidines is reported, involving the 6-exo cyclization of stabilized radicals onto alpha,beta-unsaturated esters. Only two of the four possible diastereoisomers are observed, with diastereomeric ratios ranging from 3:2 to 40:1 when the radical stabilizing group is vinyl or phenyl. Cyclization of a (triethylsilyl)vinyl-stabilized radical gives the corresponding piperidine radical as a single diastereoisomer that may either be trapped by tributyltin hydride to afford the 2,4,5-trisubstituted piperidine or undergo a second 5-endo cyclization onto the (triethylsilyl)vinyl substituent to produce the 3,5,7-trisubstituted octahydro[2]pyrindene as a single diastereoisomer.

  DOI：

  10.1021/jo101631y

文献信息

• Stereoselective Synthesis of 2,4,5-Trisubstituted Piperidines via Radical Cyclization
  作者：Maria-Eleni Ragoussi、Stephen M. Walker、Andrea Piccanello、Benson M. Kariuki、Peter N. Horton、Neil Spencer、John S. Snaith

  DOI：10.1021/jo101631y

  日期：2010.11.5

  A novel approach to 2,4,5-trisubstituted piperidines is reported, involving the 6-exo cyclization of stabilized radicals onto alpha,beta-unsaturated esters. Only two of the four possible diastereoisomers are observed, with diastereomeric ratios ranging from 3:2 to 40:1 when the radical stabilizing group is vinyl or phenyl. Cyclization of a (triethylsilyl)vinyl-stabilized radical gives the corresponding piperidine radical as a single diastereoisomer that may either be trapped by tributyltin hydride to afford the 2,4,5-trisubstituted piperidine or undergo a second 5-endo cyclization onto the (triethylsilyl)vinyl substituent to produce the 3,5,7-trisubstituted octahydro[2]pyrindene as a single diastereoisomer.