(-)-pinidinol | 55267-91-9

• 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: (-)-pinidinol
• 英文别名: 1-[(2R,6R)-6-methylpiperidin-2-yl]propan-2-ol
• CAS: 55267-91-9；55331-42-5；55331-44-7；129785-16-6；150134-95-5
• 化学式: C₉H₁₉NO
• 分子量: 157.256
• InChiKey: DVJHWTLBEYCZJZ-PSGOWDBMSA-N

物化性质

• 沸点：
  253.3±13.0 °C(Predicted)
• 密度：
  0.901±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  11
• 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：
  32.3
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (-)-pinidinol 在 次氯酸叔丁酯 、 三乙胺 作用下， 以 乙醚 、 苯 为溶剂， 反应 0.75h， 生成 (R)-6-Methyl-2-((R)-2-trimethylsilanyloxy-propyl)-2,3,4,5-tetrahydro-pyridine
  参考文献：
  名称：

  Toxic piperidine alkaloids from pine (Pinus) and spruce (Picea) trees. New structures and a biosynthetic hypothesis

  摘要：

  A series of 2,6-disubstituted piperidine alkaloids have been isolated from several Pinus (pine) and Picea (spruce) species and characterized structurally. The pines appear to contain only cis-disubstituted piperidines, while the spruces contain both cis- and trans-disubstituted piperidines. The structural relationships among the alkaloids suggest a plausible biosynthetic scheme and a reason why previous attempts to elucidate the biosynthesis of pinidine failed beyond establishing its polyketide origin. A mixture of alkaloids from needles of Pinus ponderosa proved to be highly teratogenic. The alkaloids might therefore be involved in so-called pine needle abortion which occurs in pregnant range cows which feed on Ponderosa pine needles.

  DOI：

  10.1021/jo00070a014
• 作为产物：
  描述：

  5-碘-1-戊烯 在 咪唑 、 氢氧化钾 、 sodium tetrahydroborate 、 正丁基锂 、 无水碳酸镉 、 Cp*2NdCH(SiMe₃)2 、 水 、 三苯基膦 、 mercury dichloride 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 氘代苯 、 水 、 N,N-二甲基甲酰胺 、 异丙醇 、 乙腈 为溶剂， 反应 9.0h， 生成 (-)-pinidinol
  参考文献：
  名称：

  A Diastereoselective Intramolecular Hydroamination Approach to the Syntheses of (+)-, (±)-, and (−)-Pinidinol

  摘要：

  A diastereoselective, lanthanocene-catalyzed, intramolecular hydroamination reaction was applied to the preparation of 2,6-disubstituted piperidines. Various metal/ligand arrays in the catalysts were examined using a model substrate to allow optimization of the diastereoselectivity. It was determined that the relationship between metal size and ligand bulk plays an integral role in the transformation. The complex Cp*2NdCH(TMS)(2) converted 2-substituted 8-nonen-4-amines to 2,6-disubsituted piperidines with greater than 100:1 selectivity for the formation of the cis isomer. A short synthesis of pinidinol, an alkaloid isolated from various pine and spruce species, was then carried out to exploit this stereoselective reaction.

  DOI：

  10.1021/jo015603n

文献信息

• A Highly Efficient Synthesis of (—)-Pinidinol
  作者：Siegfried Blechert、Julian Gebauer、Daniel Rost

  DOI：10.3987/com-06-10847

  日期：——

  A short step synthesis of the bioactive piperidine alkaloid (-)-pinidinol was achieved using a cross metathesis and a reductive amination as the key steps.

  使用交叉复分解和还原胺化作为关键步骤，实现了生物活性哌啶生物碱 (-)-pinidinol 的短步合成。
• A general asymmetric route to trans- or cis-2,6-disubstituted piperidine. First total synthesis of (+)-9-epi-6-epipinidinol and (−)-pinidinol
  作者：Hiroki Takahata、Yasuhito Yotsui、Takefumi Momose

  DOI：10.1016/s0040-4020(98)00831-x

  日期：1998.10

  syn-1,5-diol stereodivergently, which have been converted by aminocyclization into trans- and cis-2,6-disubstituted piperidines (trans- and cis-12), respectively. The first total synthesis of (+)-9-epi-6-epipinidinol (2) and (−)-pinidinol (3) has been achieved from trans- and cis-12.

  从1,6-庚二烯开始，两个AD反应以逐步方式逐步生成抗-1,5-二醇和syn -1,5-二醇立体异构体，它们已通过氨基环化反应转化为反式-和顺式-2,6二取代的哌啶（反式-和顺- 12），分别。9表- 6- epipinidinol（ - （+）的第一个全合成2）和（ - ） - pinidinol（3）已经从实现反式和-顺式- 12。
• Diastereocontrolled reduction of cyclic β-enaminones. A new diastereoselective route to 2,6-disubstituted piperidines
  作者：Stéphanie Fréville、Philippe Delbecq、Vu Moc Thuy、Huguette Petit、Jean Pierre Célérier、Gérard Lhommet

  DOI：10.1016/s0040-4039(01)00770-5

  日期：2001.7

  A new diastereoselective synthesis of 2,6-disubstituted piperidinic alkaloids is presented. Three natural compounds, the (−)-pinidinone 1a, the (+)-dihydropinidine 1b and the (−)-pinidinol 1c were prepared from optically pure (6R)-6-methylpiperidin-2-one 2. This method is based on the chemo- and diastereocontrolled reductions of an exocyclic β-enamino ketone.

  提出了一种新的非对映选择性合成2,6-二取代哌啶生物碱的方法。三种天然化合物中，（ - ） - pinidinone 1A中，（+） - dihydropinidine 1B pinidinol -和（ - ）1C由光学纯（6制备- [R）-6-甲基哌啶-2-酮2。该方法基于环外β-烯胺酮的化学和非对映异构控制的还原。
• A Diastereoselective Intramolecular Hydroamination Approach to the Syntheses of (+)-, (±)-, and (−)-Pinidinol
  作者：Gary A. Molander、Eric D. Dowdy、Shawn K. Pack

  DOI：10.1021/jo015603n

  日期：2001.6.1

  A diastereoselective, lanthanocene-catalyzed, intramolecular hydroamination reaction was applied to the preparation of 2,6-disubstituted piperidines. Various metal/ligand arrays in the catalysts were examined using a model substrate to allow optimization of the diastereoselectivity. It was determined that the relationship between metal size and ligand bulk plays an integral role in the transformation. The complex Cp*2NdCH(TMS)(2) converted 2-substituted 8-nonen-4-amines to 2,6-disubsituted piperidines with greater than 100:1 selectivity for the formation of the cis isomer. A short synthesis of pinidinol, an alkaloid isolated from various pine and spruce species, was then carried out to exploit this stereoselective reaction.
• Toxic piperidine alkaloids from pine (Pinus) and spruce (Picea) trees. New structures and a biosynthetic hypothesis
  作者：Jeanne N. Tawara、Andrei Blokhin、Tommaso A. Foderaro、Frank R. Stermitz、Hakon Hope

  DOI：10.1021/jo00070a014

  日期：1993.8

  A series of 2,6-disubstituted piperidine alkaloids have been isolated from several Pinus (pine) and Picea (spruce) species and characterized structurally. The pines appear to contain only cis-disubstituted piperidines, while the spruces contain both cis- and trans-disubstituted piperidines. The structural relationships among the alkaloids suggest a plausible biosynthetic scheme and a reason why previous attempts to elucidate the biosynthesis of pinidine failed beyond establishing its polyketide origin. A mixture of alkaloids from needles of Pinus ponderosa proved to be highly teratogenic. The alkaloids might therefore be involved in so-called pine needle abortion which occurs in pregnant range cows which feed on Ponderosa pine needles.