(+/-)-dihydropinidine

• 分子结构分类: 有机化合物 - 生物碱及其衍生物
• 英文名称: (+/-)-dihydropinidine
• 英文别名: (2S,6R)-2-methyl-6-propylpiperidine
• 化学式: C₉H₁₉N
• 分子量: 141.257
• InChiKey: BHBZNQCZKUGKCJ-DTWKUNHWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+/-)-dihydropinidine 在 盐酸 作用下， 以 乙醚 为溶剂， 反应 0.08h， 以96.8%的产率得到(2S,6R)-dihydropinidine hydrochloride
  参考文献：
  名称：

  Lu, Zhi-Hui; Zhou, Wei-Shen, Journal of the Chemical Society. Perkin transactions I, 1993, # 5, p. 593 - 596

  摘要：

  DOI：
• 作为产物：
  描述：

  4-氯吡啶 在 palladium on activated charcoal 正丁基锂 、 三甲基氯硅烷 、 氢气 、 lithium carbonate 、 sodium iodide 作用下， 以 四氢呋喃 、 乙酸乙酯 、 乙腈 为溶剂， 反应 15.83h， 生成 (+/-)-dihydropinidine
  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

• A highly regioselective indium-mediated allylation of pyridine derivatives: synthesis of (±)-dihydropinidine from pyridine
  作者：Teck-Peng Loh、Pek-Ling Lye、Rui-Bin Wang、Keng-Yeow Sim

  DOI：10.1016/s0040-4039(00)01332-0

  日期：2000.9

  The preparation of various 1-acyl-1,2-dihydropyridines with high regioselectivity by indium-mediated allylation of the corresponding 1-acylpyridinium salts is demonstrated. This is applied to the synthesis of (±)-dihydropinidines.

  证明了通过铟介导的相应的1-酰基吡啶鎓盐的烯丙基化制备具有高区域选择性的各种1-酰基-1,2-二氢吡啶。这适用于（±）-二氢吡啶的合成。
• Enantiocontrolled Synthesis of 2,6-Disubstituted Piperidines by Desymmetrization of <i>m</i><i>eso</i>-<i>η</i>-(3,4,5)-Dihydropyridinylmolybdenum Complexes. Application to the Total Synthesis of (−)-Dihydropinidine and (−)-Andrachcinidine
  作者：Chutian Shu、Lanny S. Liebeskind

  DOI：10.1021/ja029537y

  日期：2003.3.1

  A conceptually new approach to the enantiocontrolled synthesis of 2,6-disubstituted piperidines was achieved by desymmetrization of meso-2,6-dimethoxy-eta-(3,4,5)-dihydropyridinylmolybdenum complexes. After protection of the piperidine nitrogen as a urethane derived from (+)- or (-)-trans-2-(alpha-cumyl)cyclohexyl (TCC), a sequential, one-pot methoxide abstraction/nucleophilic addition/methoxide a

  2,6-二取代哌啶的对映控制合成的概念上新方法是通过meso-2,6-二甲氧基-eta-(3,4,5)-dihydropyridinylmolybdenum 配合物的去对称化实现的。将哌啶氮保护为衍生自 (+)- 或 (-)-trans-2-(α-枯基) 环己基 (TCC) 的氨基甲酸酯后，依次进行一锅甲醇提取/亲核加成/甲醇提取/亲核此外，2,6-二取代-eta-(3,4,5)-二氢吡啶基钼配合物的产率很高。该序列通过高度非对映选择性甲醇盐提取 (>40:1) 进行。高产量的原脱金属和 N-脱保护为各种 2,6-二取代哌啶提供了一种简单且对映控制的合成入口。
• Dearomatization of <i>N</i>-Phenyl-2,6-dialkylpiperidines: Practical Synthesis of (±)-Solenopsin A and (±)-Dihydropinidine
  作者：Jean-Pierre Hurvois、Nicolas Girard、Cyrille Gautier、Richard Malassene、Claude Moinet、Loic Toupet

  DOI：10.1055/s-2004-830884

  日期：——

  The fire ant venom alkaloid (′)-solenopsin A was prepared in 4 steps (34%) starting from the N-phenyl-2-undecyl piperidine (1c). The key step in this synthesis involved the dearomatization of the phenyl group of N-phenyl-2-methyl-6-undecyl-piperidine (9c), which was carried out under Birch conditions.

  从 N-苯基-2-十一烷基哌啶 (1c) 开始，通过 4 个步骤 (34%) 制备了火蚁毒液生物碱 (')-solenopsin A。该合成的关键步骤涉及 N-苯基-2-甲基-6-十一烷基-哌啶 (9c) 的苯基基团的脱芳构化，该步骤在 Birch 条件下进行。
• 2-cyano Δ3 piperidines vi1 : a general method for the stereoselective synthesis of cis and trans 2,6-dialkylpiperidine alkaloids
  作者：Martine Bonin、José R Romero、David S Grierson、Henri-Philippe Husson

  DOI：10.1016/s0040-4039(00)87617-0

  日期：1982.1

  The cis 2,6-dialkylpiperidine alkaloid (±) dihydro-pinidine and the trans alkaloid (±) solenopsin A were synthesized from a common α-aminonitrile synthon . The key step in this synthesis was the stereoselective reductive decyanation of the 1-benzyl-2cyano-2′, 6-dialkylpiperidines and .

  所述顺式2,6- dialkylpiperidine生物碱（±）二氢pinidine和反式生物碱（±）solenopsin甲从一个共同的α氨基腈的合成子的合成。在该合成中的关键步骤是1-苄基2cyano -2'，6- dialkylpiperidines的立体选择性还原脱氰和。
• Hydroformylation of Alkenylamines. Concise Approaches toward Piperidines, Quinolizidines, and Related Alkaloids
  作者：Etienne Airiau、Nicolas Girard、Marianna Pizzeti、Jessica Salvadori、Maurizio Taddei、André Mann

  DOI：10.1021/jo101776y

  日期：2010.12.17

  Linear hydroformylation of N-protected allyl- or homoallylamines (cyclohydrocarbonylation: CHC), followed by a reductive amination constitute the two key steps toward convenient routes to aza-heterocycles.

  N-保护的烯丙基或高烯丙基胺的线性加氢甲酰化（环氢羰基化：CHC），然后进行还原性胺化，是通往氮杂杂环便利途径的两个关键步骤。