4,4-dicarbomethoxy-3-phenyl-1,6-heptadiene | 250606-44-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 4,4-dicarbomethoxy-3-phenyl-1,6-heptadiene
• 英文别名: Dimethyl 2-(1-phenylprop-2-enyl)-2-prop-2-enylpropanedioate
• CAS: 250606-44-1
• 化学式: C₁₇H₂₀O₄
• 分子量: 288.343
• InChiKey: SNOVNYDYHIMCPY-UHFFFAOYSA-N

物化性质

• 沸点：
  333.2±37.0 °C(Predicted)
• 密度：
  1.072±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  21
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4,4-dicarbomethoxy-3-phenyl-1,6-heptadiene 在 (η³-C3H5)Pd(Cl)(PCy3) 三乙基硅烷 、 四(3,5-二(三氟甲基)苯基)硼酸钠 作用下， 以 二氯甲烷 为溶剂， 以71%的产率得到4,4-dicarbomethoxy-1,2-dimethyl-3-phenylcyclopentene
  参考文献：
  名称：

  Silane-Promoted Cycloisomerization of Functionalized 1,6-Dienes Catalyzed by a Cationic (π-Allyl)palladium Complex

  摘要：

  [GRAPHICS]A 1:1 mixture of the (pi-allyl)palladium complex (eta(3)-C3H5)Pd(Cl)PCy3 and NaB[3,5-C6H3(CF3)(2)](4) in the presence of HSiEt3 catalyzed the cycloisomerization of functionalized 1,6-dienes to form 1,2-disubstituted cyclopentenes in good yield with high selectivity (typically >94%). The protocol tolerated a range of functional groups and substitution at one of the allylic carbon atoms.

  DOI：

  10.1021/ol9908981
• 作为产物：
  描述：

  dimethyl 2-(1-phenylallyl)malonate 、 3-溴丙烯 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 2.5h， 以63%的产率得到4,4-dicarbomethoxy-3-phenyl-1,6-heptadiene
  参考文献：
  名称：

  Ni（I）催化的1,6-二烯的还原环化：机理控制的反式选择性

  摘要：

  Ni催化的1，6-二烯的还原环化得到具有高反式非对映选择性的3，4-二取代的环戊烷和吡咯烷衍生物。该环化反应使得能够有效合成反式3,4-二甲基gababutin，用于治疗神经性疼痛的药物铅，和反式- 3,4-二甲基吡咯烷，前体药物候选和杀虫剂。的反式选择性区分从经由氢原子转移和铅进行相关先例该反应的顺式产物。机械研究，包括动力学，光谱学和激进时钟研究，将反式归因于Ni（I）和Ni（III）中间体介导的经典有机金属催化循环的非对映选择性。与以前的Ni（II）催化剂观察到的氧化还原-中性环异构化相反，通过具有氧化还原活性的α-二亚胺配体稳定的富电子Ni（I）中间体对还原环化具有化学选择性。

  DOI：

  10.1016/j.chempr.2017.07.010

文献信息

• Regioselective rhodium-catalyzed allylic alkylation/ring-closing metathesis approach to carbocycles
  作者：P.Andrew Evans、Lawrence J Kennedy

  DOI：10.1016/s0040-4039(01)01467-8

  日期：2001.10

  Treatment of the allylic carbonates 1a–c with the sodium anion of the α-substituted malonates (n=0–2) and Wilkinson's catalyst modified with a triorganophosphite, furnished the allylic alkylation products 2/3a–i in 83–97% yield, favoring 2a–i. The dienes 2a–i were then subjected to ring-closing metathesis using either I or II, to afford the carbocycles 4a–i in 79–99% yield.

  用α-取代的丙二酸酯的钠阴离子（n = 0–2）和用三有机亚磷酸酯改性的威尔金森催化剂处理烯丙基碳酸盐1a – c，可以使烯丙基烷基化产物2 / 3a – i的收率达到83–97％，支持2a – i。然后使用I或II对二烯2a – i进行闭环复分解反应，从而以79–99％的收率得到碳环4a – i。
• Silane-Promoted Cycloisomerization of Functionalized 1,6-Dienes Catalyzed by a Cationic (π-Allyl)palladium Complex
  作者：Ross A. Widenhoefer、Nicholas S. Perch

  DOI：10.1021/ol9908981

  日期：1999.10.1

  [GRAPHICS]A 1:1 mixture of the (pi-allyl)palladium complex (eta(3)-C3H5)Pd(Cl)PCy3 and NaB[3,5-C6H3(CF3)(2)](4) in the presence of HSiEt3 catalyzed the cycloisomerization of functionalized 1,6-dienes to form 1,2-disubstituted cyclopentenes in good yield with high selectivity (typically >94%). The protocol tolerated a range of functional groups and substitution at one of the allylic carbon atoms.
• Development, Synthetic Scope, and Mechanistic Studies of the Palladium-Catalyzed Cycloisomerization of Functionalized 1,6-Dienes in the Presence of Silane
  作者：Philip Kisanga、Ross A. Widenhoefer

  DOI：10.1021/ja001730+

  日期：2000.10.1

  A 1:1 mixture of the pi-allyl palladium complex (eta (3)-C3H5)Pd(CI)PCy3 Cia) and NaB[3,5-C6H3(CF3)(2)](4) in the presence of HSiEt3 catalyzed the cycloisomerization of diethyl diallylmalonate (2b) to form 4,4-dicarbomethoxy 1,2-dimethylcyclopentane (3b) in 98% yield with 98% isomeric purity. The procedure tolerated a range of functionality including esters, ketones, sulfones, protected alcohols, and substitution at the allylic and terminal olefinic carbon atoms. Cycloisomerization of 2b obeyed zero-order kinetics to >3 half-lives with initial formation of 1,1-dicarboethoxy-4-methyl-3-methylenecyclopentane (4b), followed by secondary isomerization to 3b. Deuterium labeling studies revealed that the conversion of 2b to 4b was accompanied by significant H/D exchange, consistent with an addition/elimination pathway coupled with facile H/D exchange of the Pd-H(D) intermediates with free silane.
• Ni(I)-Catalyzed Reductive Cyclization of 1,6-Dienes: Mechanism-Controlled trans Selectivity
  作者：Yulong Kuang、David Anthony、Joseph Katigbak、Flaminia Marrucci、Sunita Humagain、Tianning Diao

  DOI：10.1016/j.chempr.2017.07.010

  日期：2017.8

  cyclization of 1,6-dienes affords 3,4-disubstituted cyclopentane and pyrrolidine derivatives with high trans diastereoselectivity. This cyclization reaction enables the efficient synthesis of trans-3,4-dimethyl gababutin, a pharmaceutical lead for treating neuropathic pain, and trans-3,4-dimethylpyrrolidine, a precursor to drug candidates and pesticides. The trans selectivity distinguishes this reaction

  Ni催化的1，6-二烯的还原环化得到具有高反式非对映选择性的3，4-二取代的环戊烷和吡咯烷衍生物。该环化反应使得能够有效合成反式3,4-二甲基gababutin，用于治疗神经性疼痛的药物铅，和反式- 3,4-二甲基吡咯烷，前体药物候选和杀虫剂。的反式选择性区分从经由氢原子转移和铅进行相关先例该反应的顺式产物。机械研究，包括动力学，光谱学和激进时钟研究，将反式归因于Ni（I）和Ni（III）中间体介导的经典有机金属催化循环的非对映选择性。与以前的Ni（II）催化剂观察到的氧化还原-中性环异构化相反，通过具有氧化还原活性的α-二亚胺配体稳定的富电子Ni（I）中间体对还原环化具有化学选择性。