((3R,4R)-4-methylhexa-1,5-dien-3-yl)benzene | 1338068-64-6

• 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: ((3R,4R)-4-methylhexa-1,5-dien-3-yl)benzene
• 英文别名: [(3R,4R)-4-methylhexa-1,5-dien-3-yl]benzene
• CAS: 1338068-64-6
• 化学式: C₁₃H₁₆
• 分子量: 172.27
• InChiKey: ABIBLUJJZTYFFX-DGCLKSJQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  (R)-(+)-1-phenylprop-2-yn-1-yl acetate 在 喹啉 、 tris-(dibenzylideneacetone)dipalladium(0) 、 (S)-(6,6′-二甲氧基联苯-2,2′-二基)双(二-2-呋喃基膦) 、 氢气 、 cesium fluoride 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 20.0~60.0 ℃ 、101.33 kPa 条件下， 反应 28.0h， 生成 ((3R,4R)-4-methylhexa-1,5-dien-3-yl)benzene
  参考文献：
  名称：

  Construction of 1,5-Enynes by Stereospecific Pd-Catalyzed Allyl–Propargyl Cross-Couplings

  摘要：

  The palladium-catalyzed cross-coupling of chiral propargyl acetates and allyl boronates delivers chiral 1,5-enynes with excellent levels of chirality transfer and can be applied across a broad range of substrates.

  DOI：

  10.1021/ja302329f

文献信息

• Diastereocontrol in Asymmetric Allyl–Allyl Cross-Coupling: Stereocontrolled Reaction of Prochiral Allylboronates with Prochiral Allyl Chlorides
  作者：Laura A. Brozek、Michael J. Ardolino、James P. Morken

  DOI：10.1021/ja2075967

  日期：2011.10.26

  Palladium-catalyzed allyl-ally cross-coupling was investigated with substituted prochiral allylic boronates. These reactions deliver products bearing adjacent stereocenters, and the issue of diastereocontrol is therefore paramount. Under appropriately modified conditions, this allyl allyl coupling strategy was found to apply to a range of substrates, generally occurring with high enantioselectivity (92:8 to >99:1 er) and good diastereoselection (4:1 to 14:1 dr).
• Congested C–C Bonds by Pd-Catalyzed Enantioselective Allyl–Allyl Cross-Coupling, a Mechanism-Guided Solution
  作者：Michael J. Ardolino、James P. Morken

  DOI：10.1021/ja502280w

  日期：2014.5.14

  Under the influence of a chiral bidentate diphosphine ligand, the Pd-catalyzed asymmetric cross-coupling of allylboron reagents and allylic electrophiles establishes 1,5-dienes with adjacent stereocenters in high regio- and stereoselectivity. A mechanistic study of the coupling utilizing reaction calorimetry and density functional theory analysis suggests that the reaction operates through an inner-sphere 3,3'-reductive elimination pathway, which is both rate-defining and stereodefining. Coupled with optimized reaction conditions, this mechanistic detail is used to expand the scope of allyl allyl couplings to allow the generation of 1,5-dienes with tertiary centers adjacent to quaternary centers as well as a unique set of cyclic structures.