dimethyl di(2,4-pentadienyl)propanedioate | 463305-00-2

• 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: dimethyl di(2,4-pentadienyl)propanedioate
• 英文别名: dimethyl 2,2-bis[(2E)-penta-2,4-dienyl]propanedioate
• CAS: 463305-00-2
• 化学式: C₁₅H₂₀O₄
• 分子量: 264.321
• InChiKey: VHLUGYCEOREPTJ-FIFLTTCUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  19
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  dimethyl di(2,4-pentadienyl)propanedioate 在 bis(acetylacetonate)nickel(II) lithium aluminium tetrahydride 、 臭氧 、 三苯基膦 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 正戊烷 为溶剂， -78.0~40.0 ℃ 、101.33 kPa 条件下， 反应 71.0h， 生成 (R)-2-((1S,2S)-2-Hydroxymethyl-4,4-bis-methoxymethyl-cyclopentyl)-3-methoxy-propan-1-ol
  参考文献：
  名称：

  新型催化 CO2 掺入反应：双 1,3-二烯的镍催化区域和立体选择性闭环羧化

  摘要：

  研究了使用二氧化碳 (CO2) 对双 1,3-二烯进行新型镍催化羧化反应。在催化量的 Ni(acac)2 和 PPh3 存在下，各种双 1,3-二烯在温和条件下与 CO2 和有机锌试剂（Et2Zn、Me2Zn 或 Ph2Zn）顺利反应。这种催化羧化过程伴随着双-1,3-二烯的碳环化，然后通过有机锌试剂进行烷基化，以高产率和高区域选择性和立体选择性提供环状羧酸衍生物。

  DOI：

  10.1021/ja026620c
• 作为产物：
  描述：

  1,3-戊二烯,5-溴- 、 丙二酸二甲酯 在 sodium hydride 作用下， 生成 2-(2,4-戊二烯基)丙二酸二甲酯 、 dimethyl di(2,4-pentadienyl)propanedioate
  参考文献：
  名称：

  (Phenylsulfonyl)allenes as Substrates for Cycloaddition Reactions: Intramolecular Cyclizations onto Unactivated Alkenes

  摘要：

  The reaction of a series of allyl-substituted bis(phenylsulfonyl)methanes or dimethyl malonates with 2,3-bis(phenylsulfonyl)-1,3-butadiene in the presence of base afforded alkenyl-substituted allenes in good yield. The reaction proceeds by initial attack of the soft carbanion onto the terminal position of the diene, and this is followed by PhSO(2)(-) elimination to give the phenylsulfonyl-substituted allene. Themal [2 + 2]-cycloaddition proceeded across the C-1-C-2 double bond of the allene with completely sterospecificity. Stepwise bonding prefers to occur in a 1,6-exo manner rather than in a 1,7-endo fashion. Substitution at the 7-position of the pi-bond causes a crossover in the regioselectivity of the [2 + 2]-cycloaddition process. All products can be rationalized by a mechanism which includes an initial carbon-carbon bond formation involving the central allene carbon to give a diradical intermediate. The product distribution is then determined by the substitution pattern of the alkene and the fate of the diradical intermediate.

  DOI：

  10.1021/ja00132a005

文献信息

• Highly Enantioselective Catalytic Carbon Dioxide Incorporation Reaction:  Nickel-Catalyzed Asymmetric Carboxylative Cyclization of Bis-1,3-dienes
  作者：Masanori Takimoto、Yoichi Nakamura、Kaoru Kimura、Miwako Mori

  DOI：10.1021/ja049506y

  日期：2004.5.1

  A method for nickel-catalyzed asymmetric carbon dioxide (CO2) incorporation via carbon-carbon bond formation was developed. In the presence of a catalytic amount of Ni(acac)2 and MeO-MOP, various bis-1,3-dienes reacted with CO2 (1 atm) and a diorganozinc reagent (Me2Zn or Ph2Zn) to afford cyclic carboxylic acids in good yields (71-100%) and with high enantioselectivities (90-96% ee).

  开发了一种通过碳-碳键形成的镍催化不对称二氧化碳 (CO2) 掺入的方法。在催化量的 Ni(acac)2 和 MeO-MOP 存在下，各种双 1,3-二烯与 CO2 (1 atm) 和二有机锌试剂（Me2Zn 或 Ph2Zn）反应，以良好的收率得到环状羧酸(71-100%) 和高对映选择性 (90-96% ee)。
• Nickel-Catalyzed Enantioselective Three-Component Coupling of Bis-1,3-dienes, Aldehydes, and Dimethylzinc
  作者：Masanori Takimoto、Yuuki Kajima、Yoshihiro Sato、Miwako Mori

  DOI：10.1021/jo051283m

  日期：2005.10.1

  bis-1,3-dienes, aldehyde, and dimethylzinc was investigated. In the presence of catalytic amounts of Ni(acac)2 and PPh3, bis-1,3-dienes smoothly react with an aldehyde and dimethylzinc via intramolecular cyclodimerization of bis-1,3-diene moiety. The reaction proceeds through formation of a cyclic bis-allylnickel complex, insertion of an aldehyde, and addition of dimethylzinc to the resulting oxanickellacycle

  研究了双-1,3-二烯，醛和二甲基锌的镍催化三组分偶联。在催化量的Ni（acac）2和PPh 3的存在下，双-1,3-二烯通过双-1,3-二烯部分的分子内环二聚反应与醛和二甲基锌平稳反应。该反应通过形成环状双烯丙基镍络合物，插入醛和将二甲基锌添加至所得的氧杂ick环中间体而进行。对映选择性偶联也通过使用手性单齿膦配体H-MOP来实现。
• TAKACS, JAMES M.;ZHU, JINGYANG, J. ORG. CHEM., 54,(1989) N2, C. 5193-5195
  作者：TAKACS, JAMES M.、ZHU, JINGYANG

  DOI：——

  日期：——
• (Phenylsulfonyl)allenes as Substrates for Cycloaddition Reactions: Intramolecular Cyclizations onto Unactivated Alkenes
  作者：Albert Padwa、Michael Meske、S. Shaun Murphree、Scott H. Watterson、Zhijie Ni

  DOI：10.1021/ja00132a005

  日期：1995.7

  The reaction of a series of allyl-substituted bis(phenylsulfonyl)methanes or dimethyl malonates with 2,3-bis(phenylsulfonyl)-1,3-butadiene in the presence of base afforded alkenyl-substituted allenes in good yield. The reaction proceeds by initial attack of the soft carbanion onto the terminal position of the diene, and this is followed by PhSO(2)(-) elimination to give the phenylsulfonyl-substituted allene. Themal [2 + 2]-cycloaddition proceeded across the C-1-C-2 double bond of the allene with completely sterospecificity. Stepwise bonding prefers to occur in a 1,6-exo manner rather than in a 1,7-endo fashion. Substitution at the 7-position of the pi-bond causes a crossover in the regioselectivity of the [2 + 2]-cycloaddition process. All products can be rationalized by a mechanism which includes an initial carbon-carbon bond formation involving the central allene carbon to give a diradical intermediate. The product distribution is then determined by the substitution pattern of the alkene and the fate of the diradical intermediate.
• Novel Catalytic CO₂ Incorporation Reaction:  Nickel-Catalyzed Regio- and Stereoselective Ring-Closing Carboxylation of Bis-1,3-dienes
  作者：Masanori Takimoto、Miwako Mori

  DOI：10.1021/ja026620c

  日期：2002.8.1

  Novel nickel-catalyzed carboxylation of bis-1,3-dienes using carbon dioxide (CO2) was investigated. In the presence of catalytic amounts of Ni(acac)2 and PPh3, various bis-1,3-dienes smoothly reacted with CO2 and an organozinc reagent (Et2Zn, Me2Zn, or Ph2Zn) under mild conditions. This catalytic carboxylation process was accompanied by carbocyclization of bis-1,3-diene followed by alkylation by an

  研究了使用二氧化碳 (CO2) 对双 1,3-二烯进行新型镍催化羧化反应。在催化量的 Ni(acac)2 和 PPh3 存在下，各种双 1,3-二烯在温和条件下与 CO2 和有机锌试剂（Et2Zn、Me2Zn 或 Ph2Zn）顺利反应。这种催化羧化过程伴随着双-1,3-二烯的碳环化，然后通过有机锌试剂进行烷基化，以高产率和高区域选择性和立体选择性提供环状羧酸衍生物。