dimethyl 2-[(E)-4,4-diacetyloxybut-2-enyl]-2-prop-2-ynylpropanedioate | 108561-12-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: dimethyl 2-[(E)-4,4-diacetyloxybut-2-enyl]-2-prop-2-ynylpropanedioate
• CAS: 108561-12-2
• 化学式: C₁₆H₂₀O₈
• 分子量: 340.33
• InChiKey: DPOUWMQEUZNPHD-BQYQJAHWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  24
• 可旋转键数：
  12
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  105
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  dimethyl 2-[(E)-4,4-diacetyloxybut-2-enyl]-2-prop-2-ynylpropanedioate 在 双(乙腈)氯化钯(II) 、 lithium chloride 、 copper dichloride 作用下， 以 溶剂黄146 、 乙腈 为溶剂， 反应 0.5h， 以97%的产率得到3-((E)-2-Acetoxy-vinyl)-4-[1-chloro-meth-(Z)-ylidene]-cyclopentane-1,1-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  Palladium-catalysed cyclisation and functionalisation of 1,1-diacetoxy-2,7-diene and 1,1-diacetoxy-2-en-7-yne derivatives

  摘要：

  The palladium-catalysed 'metallo-ene' cyclisation, cyclisation/carbonylation, -vinylstannane coupling, and Pd(II)-catalysed chloropalladation/carbocyclisation of 1,1-diacetoxy-2,7-diene and 1,1-diacetoxy-2-en-7-yne derivatives are described. The cyclic enolacetate products could readily be converted into the corresponding aldehydes that are amenable to further transformation. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)00169-5
• 作为产物：
  描述：

  γ-Brom-crotonaldehyd-diacetat 、 炔丙基丙二酸二甲酯 在 sodium hydride 作用下， 生成 dimethyl 2-[(E)-4,4-diacetyloxybut-2-enyl]-2-prop-2-ynylpropanedioate
  参考文献：
  名称：

  Pd-Catalyzed Cycloisomerization to 1,2-Dialkylidenecycloalkanes. 2. Alternative Catalyst System

  摘要：

  The mechanisms by which palladium complexes may catalyze the cycloisomerization of 1,6- and 1,7-enynes to dialkylidenecycloalkanes were probed by exploring a catalyst system different than a ligated palladium acetate which previously has proven to be successful. Although carboxylic acids showed no discernible interaction with palladium(0) complexes, this combination proved to be a powerful catalyst system to effect this cycloisomerization. The fact that the two catalyst systems do not have the same reactivity profile suggests this new catalyst system may operate by a different mechanism. Evidence supporting a pathway invoking formation of a hydridopalladium acetate followed by hydropalladation as initiation is presented. Steric and electronic effects direct the regioselectivity of the termination step to form either 1,3- or 1,4-diene products. The 1,3-diene products participate exceedingly well in Diels-Alder reactions, both inter- and intramolecularly. The presence of an oxygen substituent at the position allylic to the diene served as both a regiochemical control element for the palladium-catalyzed cycloisomerization and a diastereochemical control element for the Diels-Alder reaction. The net result of these two steps, the first of which is a catalyzed isomerization and the second an addition, is a highly efficient approach to complex polycycles in terms of both selectivity and atom economy.

  DOI：

  10.1021/ja00089a016

文献信息

• Reductive cyclization of 1,6- and 1,7-enynes
  作者：Barry M. Trost、Frode Rise

  DOI：10.1021/ja00244a059

  日期：1987.5
• TROST, BARRY M.;LEE, DONNA C.;RISE, FRODE, TETRAHEDRON LETT., 30,(1989) N, C. 651-654
  作者：TROST, BARRY M.、LEE, DONNA C.、RISE, FRODE

  DOI：——

  日期：——
• TROST B. M.; RISE F., J. AMER. CHEM. SOC., 109,(1987) N 10, 3161-3163
  作者：TROST B. M.、 RISE F.

  DOI：——

  日期：——