1-(tert-butoxycarbonyl)-4-chloro-trans-2-methyl-6-n-undecyl-1,2,5,6-tetrahydropyridine | 132410-13-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 1-(tert-butoxycarbonyl)-4-chloro-trans-2-methyl-6-n-undecyl-1,2,5,6-tetrahydropyridine
• 英文别名: tert-butyl (2R,6R)-4-chloro-6-methyl-2-undecyl-3,6-dihydro-2H-pyridine-1-carboxylate
• CAS: 132410-13-0
• 化学式: C₂₂H₄₀ClNO₂
• 分子量: 386.018
• InChiKey: ZMNSVBLUZPHQJO-UYAOXDASSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.2
• 重原子数：
  26
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-(tert-butoxycarbonyl)-4-chloro-trans-2-methyl-6-n-undecyl-1,2,5,6-tetrahydropyridine 在 palladium on activated charcoal 氢气 、 lithium carbonate 作用下， 以 乙醇 为溶剂， 反应 12.0h， 以80%的产率得到tert-butyl (2R,6R)-2-methyl-6-undecylpiperidinecarboxylate
  参考文献：
  名称：

  Stereocontrolled preparation of cis- and trans-2,6-dialkylpiperidines via 1-acyldihydropyridine intermediates. Synthesis of (.+-.)-solenopsin A and (.+-.)-dihydropinidine

  摘要：

  The stereoselective reduction of 1-(tert-butoxycarbonyl)-4-chloro-2,6-dialkyl-1,2-dihydropyridines 6 and 22 was studied. Reduction of 6 with Et3SiH/TFA gave the cis-2,6-dialkyl-1,2,5,6-tetrahydropyridine 7 as the major product. The stereoselectivity was reversed by reducing 6 with NaBH3CN/TFA, which gave predominantly the trans-2,6-dialkyltetrahydropyridine 10. Catalytic hydrogenation of 7 and 10 gave the corresponding N-Boc-cis(or trans)-2,6-dialkylpiperidines. Regioselective hydrogenation of 6 gave the 1,2,3,4-tetrahydropyridine 18, which on treatment with NaBH3CN/TFA provided a 90:10 mixture of trans- and cis-piperidines 15 and 16. More vigorous hydrogenation of 6 afforded the cis-piperidine 15 with 96% stereoselectivity. Similar stereoselective reductions of dihydropyridine 22 were carried out. Stereoselective reductions of dihydropyridines 6 and 22 were utilized in the synthesis of (+/-)-solenopsin A and (+/-)-dihydropinidine from 4-chloropyridine in six and five steps, respectively.

  DOI：

  10.1021/jo00007a044
• 作为产物：
  描述：

  1-溴十一烷 在 三乙基硅烷 、 正丁基锂 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 8.0h， 生成 1-(tert-butoxycarbonyl)-4-chloro-trans-2-methyl-6-n-undecyl-1,2,5,6-tetrahydropyridine
  参考文献：
  名称：

  Stereocontrolled preparation of cis- and trans-2,6-dialkylpiperidines via 1-acyldihydropyridine intermediates. Synthesis of (.+-.)-solenopsin A and (.+-.)-dihydropinidine

  摘要：

  The stereoselective reduction of 1-(tert-butoxycarbonyl)-4-chloro-2,6-dialkyl-1,2-dihydropyridines 6 and 22 was studied. Reduction of 6 with Et3SiH/TFA gave the cis-2,6-dialkyl-1,2,5,6-tetrahydropyridine 7 as the major product. The stereoselectivity was reversed by reducing 6 with NaBH3CN/TFA, which gave predominantly the trans-2,6-dialkyltetrahydropyridine 10. Catalytic hydrogenation of 7 and 10 gave the corresponding N-Boc-cis(or trans)-2,6-dialkylpiperidines. Regioselective hydrogenation of 6 gave the 1,2,3,4-tetrahydropyridine 18, which on treatment with NaBH3CN/TFA provided a 90:10 mixture of trans- and cis-piperidines 15 and 16. More vigorous hydrogenation of 6 afforded the cis-piperidine 15 with 96% stereoselectivity. Similar stereoselective reductions of dihydropyridine 22 were carried out. Stereoselective reductions of dihydropyridines 6 and 22 were utilized in the synthesis of (+/-)-solenopsin A and (+/-)-dihydropinidine from 4-chloropyridine in six and five steps, respectively.

  DOI：

  10.1021/jo00007a044

文献信息

• Stereocontrolled preparation of cis- and trans-2,6-dialkylpiperidines via 1-acyldihydropyridine intermediates. Synthesis of (.+-.)-solenopsin A and (.+-.)-dihydropinidine
  作者：Daniel L. Comins、Michael A. Weglarz

  DOI：10.1021/jo00007a044

  日期：1991.3

  The stereoselective reduction of 1-(tert-butoxycarbonyl)-4-chloro-2,6-dialkyl-1,2-dihydropyridines 6 and 22 was studied. Reduction of 6 with Et3SiH/TFA gave the cis-2,6-dialkyl-1,2,5,6-tetrahydropyridine 7 as the major product. The stereoselectivity was reversed by reducing 6 with NaBH3CN/TFA, which gave predominantly the trans-2,6-dialkyltetrahydropyridine 10. Catalytic hydrogenation of 7 and 10 gave the corresponding N-Boc-cis(or trans)-2,6-dialkylpiperidines. Regioselective hydrogenation of 6 gave the 1,2,3,4-tetrahydropyridine 18, which on treatment with NaBH3CN/TFA provided a 90:10 mixture of trans- and cis-piperidines 15 and 16. More vigorous hydrogenation of 6 afforded the cis-piperidine 15 with 96% stereoselectivity. Similar stereoselective reductions of dihydropyridine 22 were carried out. Stereoselective reductions of dihydropyridines 6 and 22 were utilized in the synthesis of (+/-)-solenopsin A and (+/-)-dihydropinidine from 4-chloropyridine in six and five steps, respectively.