2-[(1S,2S,3S,4R)-2-((1R,2S,5R)-2-Isopropyl-5-methyl-cyclohexyl)-2-phospha-bicyclo[2.2.1]hept-5-en-3-yl]-pyridine | 137466-71-8

• 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: 2-[(1S,2S,3S,4R)-2-((1R,2S,5R)-2-Isopropyl-5-methyl-cyclohexyl)-2-phospha-bicyclo[2.2.1]hept-5-en-3-yl]-pyridine
• CAS: 137466-71-8
• 化学式: C₂₁H₃₀NP
• 分子量: 327.45
• InChiKey: IECNBUCRDVBAAO-GSFDJTBLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.02
• 重原子数：
  23.0
• 可旋转键数：
  3.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  12.89
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  吡啶-2-甲醛 、 L-menthyldichlorophosphine 、 环戊二烯 生成 2-[(1S,2S,3S,4R)-2-((1R,2S,5R)-2-Isopropyl-5-methyl-cyclohexyl)-2-phospha-bicyclo[2.2.1]hept-5-en-3-yl]-pyridine
  参考文献：
  名称：

  Use of prochiral phosphaalkene complexes in the synthesis of optically active phosphines

  摘要：

  Prochiral L-Menthyl phosphaalkene complexes were prepared from ''phospha-Wittig'' reagents, [MenP(H)-P-(O) (OR)2]M(CO)5 (M = Mo, W), and several aldehydes. Their catalytic hydrogenation using RhL2+ catalysts and their [2 + 4] cycloaddition with cyclopentadiene proceeded with full diastereoselectivity. A molecular model of such a phosphaalkene complex showed that a preferred conformation exists that minimizes the combined interactions of the isopropyl substituent of the L-menthyl group with the complexing group and the phosphavinylic C-H bond. In this conformation, only the si face of the phosphaalkene is free for the incoming reagents. Both hydrogenation and [2 + 4] cycloaddition with cyclopentadiene selectively take place on this face as demonstrated by the X-ray crystal structure analysis of two of the resulting complexes. A two-step procedure was devised for the conversion of [MenPH2]Mo(CO)5 into optically pure phosphines. In the first step, the primary phosphine complex was phosphorylated, the resulting phospha-Wittig reagent was allowed to react with an aldehyde, and the phosphaalkene complex thus formed was trapped by cyclopentadiene. The decomplexation of the resulting molybdenum complex was carried out by heating with diphos. An optically pure 2-L-menthyl-2-phospha-5-norbornene was thus prepared.

  DOI：

  10.1021/ja00027a034