4-Methoxy-1-[(1R,2S,5R)-5-methyl-2-(1-methyl-1-phenyl-ethyl)-cyclohexyloxycarbonyl]-3-triisopropylsilanyl-pyridinium; chloride | 144375-66-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 4-Methoxy-1-[(1R,2S,5R)-5-methyl-2-(1-methyl-1-phenyl-ethyl)-cyclohexyloxycarbonyl]-3-triisopropylsilanyl-pyridinium; chloride
• 英文别名: [(1R,2S,5R)-5-methyl-2-(2-phenylpropan-2-yl)cyclohexyl] 4-methoxy-3-tri(propan-2-yl)silylpyridin-1-ium-1-carboxylate;chloride
• CAS: 144375-66-6
• 化学式: C₃₂H₅₀NO₃Si*Cl
• 分子量: 560.292
• InChiKey: VHHXWFWCRMFZMG-RTXDGLNOSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  4.64
• 重原子数：
  38
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  39.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-Methoxy-1-[(1R,2S,5R)-5-methyl-2-(1-methyl-1-phenyl-ethyl)-cyclohexyloxycarbonyl]-3-triisopropylsilanyl-pyridinium; chloride 在 palladium on activated charcoal 、 platinum on activated charcoal 正丁基锂 、 氢气 、 sodium methylate 、 草酸 、 lithium carbonate 、 N,N-二甲基甲酰胺 、 三氯氧磷 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 乙醇 、 正己烷 、 三氯乙烯 为溶剂， 反应 37.0h， 生成 (R)-2-丙基哌啶
  参考文献：
  名称：

  Conversion of N-acyl-2,3-dihydro-4-pyridones to 4-chloro-1,2-dihydropyridines using the Vilsmeier Reagent. Synthesis of (-)-coniine and (±)-lupinine

  摘要：

  The full details are given of a study on the conversion of dihydropyridones of the type 3 to 4-chloro-1,2-dihydropyridines 4 using a Vilsmeier reagent. The use of 1 equiv of Vilsmeier reagent under mild conditions (ClCHCCl2, rt) transformed several racemic N-acyl-2,3-dihydro-4-pyridones 3 to dihydropyridines 4 in very good to excellent yields (83-96%). A C-3 methyl group can be tolerated as was demonstrated in the preparation of 4-chloro-3-methyl-1,2-dihydropyridine 7 from dihydropyridone 6 in 90 % yield. The utility of this conversion was demonstrated in the synthesis of the piperidine alkaloid, (-)-coniine. The synthesis of (-)-coniine was completed in five steps from 4-methoxy-3-(triisopropylsilyl)pyridine in 54% overall yield. When 2,3-dihydro-4-pyridones are treated with excess Vilsmeier reagent, good yields of 4-chloro-3-formyl-1,2-dihydropyridines result. These heterocycles are useful intermediates for alkaloid preparation, as was shown by two syntheses of the quinolizidine alkaloid, (+/-)-lupinine, carried out in three and five steps, respectively.

  DOI：

  10.1021/jo00079a018
• 作为产物：
  描述：

  4-甲氧基-3-(三异丙基甲硅烷基)嘧啶 、 (1R,2S,5R)-(-)-8-phenylmenthyl chloroformate 以 甲苯 为溶剂， 反应 0.75h， 生成 4-Methoxy-1-[(1R,2S,5R)-5-methyl-2-(1-methyl-1-phenyl-ethyl)-cyclohexyloxycarbonyl]-3-triisopropylsilanyl-pyridinium; chloride
  参考文献：
  名称：

  Conversion of N-acyl-2,3-dihydro-4-pyridones to 4-chloro-1,2-dihydropyridines using the Vilsmeier Reagent. Synthesis of (-)-coniine and (±)-lupinine

  摘要：

  The full details are given of a study on the conversion of dihydropyridones of the type 3 to 4-chloro-1,2-dihydropyridines 4 using a Vilsmeier reagent. The use of 1 equiv of Vilsmeier reagent under mild conditions (ClCHCCl2, rt) transformed several racemic N-acyl-2,3-dihydro-4-pyridones 3 to dihydropyridines 4 in very good to excellent yields (83-96%). A C-3 methyl group can be tolerated as was demonstrated in the preparation of 4-chloro-3-methyl-1,2-dihydropyridine 7 from dihydropyridone 6 in 90 % yield. The utility of this conversion was demonstrated in the synthesis of the piperidine alkaloid, (-)-coniine. The synthesis of (-)-coniine was completed in five steps from 4-methoxy-3-(triisopropylsilyl)pyridine in 54% overall yield. When 2,3-dihydro-4-pyridones are treated with excess Vilsmeier reagent, good yields of 4-chloro-3-formyl-1,2-dihydropyridines result. These heterocycles are useful intermediates for alkaloid preparation, as was shown by two syntheses of the quinolizidine alkaloid, (+/-)-lupinine, carried out in three and five steps, respectively.

  DOI：

  10.1021/jo00079a018

文献信息

• A short, asymmetric synthesis of (–)-pumiliotoxin C
  作者：Daniel L. Comins、All Dehghani

  DOI：10.1039/c39930001838

  日期：——

  An asymmetric synthesis of (–)-pumiliotoxin C is accomplished in nine steps from 4-methoxy-3-(triisopropylsilyl)pyridine.

  以4-甲氧基-3-(三异丙基硅基)吡啶为原料，经九步反应实现了(−)-普米利毒素C的不对称合成。
• The addition of metallo enolates to chiral 1-acylpyridinium salts. An asymmetric synthesis of (-)-sedamine
  作者：Daniel L. Comins、Hao Hong

  DOI：10.1021/jo00071a005

  日期：1993.9

  Synthetically useful 2-(2-oxoalkyl)-2,3-dihydro-4-pyridones are prepared in high diastereomeric excess by addition of ketone metallo enolates to chiral 1-acyl-4-methoxypyridinium salts.
• An efficient asymmetric synthesis of 1-acyl-2-alkyl-1,2-dihydropyridines
  作者：Daniel L. Comins、Hao Hong、James M. Salvador

  DOI：10.1021/jo00026a004

  日期：1991.12

  Two efficient chiral auxiliary mediated asymmetric syntheses of synthetically useful 1-acyl-2-alkyl-1,2-dihydropyridines are described.
• Enantiopure 2,3-dihydro-4-pyridones as synthetic intermediates. Asymmetric syntheses of the quinolizidine alkaloids, (+)-myrtine, (-)-lasubine I, and (+)-subcosine I
  作者：Daniel L. Comins、Donald H. LaMunyon

  DOI：10.1021/jo00048a003

  日期：1992.10

  The first asymmetric syntheses of three quinolizidine alkaloids, (+)-myrtine, (-)-lasubine I, and (+)-subcosine I, were accomplished with a high degree of stereocontrol from readily available 4-methoxy-3-(triisopropylsilyl)pyridine in three, four, and five steps, respectively.
• Asymmetric synthesis of (-)-porantheridine
  作者：Daniel L. Comins、Hao Hong

  DOI：10.1021/ja00072a053

  日期：1993.9