(3S)-3-methyl-5-phenyl-1-pentyne | 1234490-12-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (3S)-3-methyl-5-phenyl-1-pentyne
• 英文别名: [(3S)-3-methylpent-4-ynyl]benzene
• CAS: 1234490-12-0
• 化学式: C₁₂H₁₄
• 分子量: 158.243
• InChiKey: RJXBOJYUPRLXOV-LLVKDONJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (3S)-3-methyl-5-phenyl-1-pentyne 在 palladium on carbon 、 氢气 作用下， 生成 (-)(R)-3-methyl-1-phenyl-pentane
  参考文献：
  名称：

  SN2-Selective allylic substitution of chiral γ-aryl substituted allylic picolinates with alkynylcopper reagents

  摘要：

  Substitution of gamma-aryl secondary allylic picolinates with alkynyl copper reagents was studied. The copper reagent, prepared from TMSC equivalent to CMgBr and CuBr center dot Me-25 in 2:1, was subjected to substitution of the picolinate derived from (E)-3-phenyl-1-methyl-2-propenyl alcohol at 0 degrees C for 1 h in THF to produce a mixture of alpha- and gamma-products and the alcohol in 67:20:13, while the reagent in 3 or 4:1 ratio gave the alpha-product with 90-91% selectivity. On the contrary, reaction in CH2Cl2-THF (6-8:1) at 0 degrees C for 1 h furnished the alpha-product with 99% regioselectivity. The effect of CH2Cl2 was also demonstrated with eight more examples. Furthermore, 99% inversion was determined by transformation to the literature compound and by chiral H PLC. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2010.08.051
• 作为产物：
  描述：

  在 Wilkinson's catalyst 、 氢气 作用下， 生成 (3S)-3-methyl-5-phenyl-1-pentyne
  参考文献：
  名称：

  SN2-Selective allylic substitution of chiral γ-aryl substituted allylic picolinates with alkynylcopper reagents

  摘要：

  Substitution of gamma-aryl secondary allylic picolinates with alkynyl copper reagents was studied. The copper reagent, prepared from TMSC equivalent to CMgBr and CuBr center dot Me-25 in 2:1, was subjected to substitution of the picolinate derived from (E)-3-phenyl-1-methyl-2-propenyl alcohol at 0 degrees C for 1 h in THF to produce a mixture of alpha- and gamma-products and the alcohol in 67:20:13, while the reagent in 3 or 4:1 ratio gave the alpha-product with 90-91% selectivity. On the contrary, reaction in CH2Cl2-THF (6-8:1) at 0 degrees C for 1 h furnished the alpha-product with 99% regioselectivity. The effect of CH2Cl2 was also demonstrated with eight more examples. Furthermore, 99% inversion was determined by transformation to the literature compound and by chiral H PLC. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2010.08.051

文献信息

• Nickel-Catalyzed Asymmetric Addition of Alkyne CH Bonds across 1,3-Dienes Using Taddol-Based Chiral Phosphoramidite Ligands
  作者：Masamichi Shirakura、Michinori Suginome

  DOI：10.1002/anie.201001188

  日期：——

  Enantioenriched 3‐methyl‐1,4‐enynes are the products of the title reaction. The terminal α‐siloxy‐sec‐alkyl groups were then converted into γ‐oxoalkyl groups by rhodium‐catalyzed conjugate alkynyl addition to α,β‐unsaturated ketones through cleavage of the alkynyl CC bond.

  对映体富集的3-甲基-1,4-烯炔是标题反应的产物。然后，通过裂解炔基C addition C键，将铑催化的共轭炔基加成α，β-不饱和酮，将末端α-甲硅烷氧基仲烷基转化为γ-氧代烷基。