(2S,6R)-1-tert-butoxycarbonyl-6-methyl-2-propylpiperidine | 184535-11-3

• 分子结构分类: 有机化合物 - 生物碱及其衍生物
• 英文名称: (2S,6R)-1-tert-butoxycarbonyl-6-methyl-2-propylpiperidine
• 英文别名: (2R,6R)-2-propyl-6-methylpiperidine-1-carboxylic acid tert-butyl ester；tert-butyl (2R,6R)-2-methyl-6-propylpiperidine-1-carboxylate
• CAS: 184535-11-3
• 化学式: C₁₄H₂₇NO₂
• 分子量: 241.374
• InChiKey: VUYCICJKIMXBKT-VXGBXAGGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 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：

  (2S,6R)-1-tert-butoxycarbonyl-6-methyl-2-propylpiperidine 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以99%的产率得到(+)-trans-2-methyl-6-propylpiperidine
  参考文献：
  名称：

  2-甲基哌啶的分离度提高及其在同手性反式-2,6-二烷基哌啶合成中的应用

  摘要：

  摘要 描述了一种拆分 2-甲基哌啶的有效方法。对映异构体用于快速有效地合成 C2 对称哌啶、(+)-lupetidine 和 (+)-epidihydropinidine。

  DOI：

  10.1080/00397919908086162
• 作为产物：
  描述：

  4-氯吡啶 在 palladium on activated charcoal 正丁基锂 、 氢气 、 lithium carbonate 作用下， 以 四氢呋喃 、 乙酸乙酯 为溶剂， 反应 3.83h， 生成 (2S,6R)-1-tert-butoxycarbonyl-6-methyl-2-propylpiperidine
  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

• An Improved Resolution Of 2-Methyl Piperidine And Its Use in The Synthesis Of Homochiral Trans-2,6-Dialkyl Piperidines
  作者：Mauro F. A. Adamo、Varinder K. Aggarwal、Matthew A. Sage

  DOI：10.1080/00397919908086162

  日期：1999.5

  Abstract An efficient procedure for the resolution of 2-methylpiperidine is described. The enantiomers were used for a short and effective synthesis of the C2 symmetric piperidine, (+)-lupetidine and (+)-epidihydropinidine.

  摘要 描述了一种拆分 2-甲基哌啶的有效方法。对映异构体用于快速有效地合成 C2 对称哌啶、(+)-lupetidine 和 (+)-epidihydropinidine。
• A new asymmetric entry to 2-substituted piperidines. A concise synthesis of (+)-coniine, (−)-pelletierine, (+)-δ-coniceine, and (+)-epidihydropinidine
  作者：Hiroki Takahata、Minoru Kubota、Seiki Takahashi、Takefumi Momose

  DOI：10.1016/0957-4166(96)00395-3

  日期：1996.10

  A new asymmetric route to 2-substituted piperidines involving the Sharpless asymmetric dihydroxylation (AD) of 5-hexenylazide 1 and an intramolecular aminocyclization as crucial steps and its application to the asymmetric synthesis of four piperidine alkaloids, (+)-coniine 2, (−)-pelletierine 3, (+)-δ-coniceine 4, and (+)-epidihydropinidine 5 is presented.

  涉及5-己烯基叠氮化物1的Sharpless不对称二羟基化（AD）和分子内氨基环化作为关键步骤的2取代哌啶的新不对称路线及其在四个哌啶生物碱（+）-coniine 2的不对称合成中的应用，（-呈现了）-Peltierine 3，（+）-δ-可卡因4和（+）-epidihydropinidine 5。
• 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.
• Enantiopure N-Boc piperidine-2-ethanol for the synthesis of (+)- and (−)-dumetorine, and (+)- and (−)-epidihydropinidine
  作者：Daniele Passarella、Sergio Riva、Gabriele Grieco、Francesco Cavallo、Begoña Checa、Federica Arioli、Elena Riva、Daniela Comi、Bruno Danieli

  DOI：10.1016/j.tetasy.2008.12.008

  日期：2009.2

  The convenient synthesis of both enantiomers of the piperidine alkaloids such as dumetorine and epidihydropinidine is described. Pure enantiomers of 2-(2-hydroxy-ethyl)-piperidine-1-carboxylic acid tert-butyl ester are used as a common starting material. The syntheses are based on a RCM reaction and on methylation of the piperidine ring according to Beak-Lee methodology, respectively. (C) 2008 Elsevier Ltd. All rights reserved