dimethyl 2-(4'-acetoxybut-2'(Z)-enyl)malonate | 85669-67-6

• 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 2-(4'-acetoxybut-2'(Z)-enyl)malonate
• 英文别名: dimethyl (4-acetoxy-2(Z)-butenyl)propanedioate；Dimethyl (Z)-(4-acetoxybut-2-en-1-yl)malonate；methyl 5-acetoxy-2-(methoxycarbonyl)-(3Z)-pentenoate；(Z)-methyl-6-acetoxy-2-(methoxycarbonyl)-hex-4-enoate；dimethyl 2-[(Z)-4-acetyloxybut-2-enyl]propanedioate
• CAS: 85669-67-6
• 化学式: C₁₁H₁₆O₆
• 分子量: 244.244
• InChiKey: YMDKLMKWKPITCB-PLNGDYQASA-N

物化性质

• 沸点：
  297.9±40.0 °C(Predicted)
• 密度：
  1.138±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  17
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  dimethyl 2-(4'-acetoxybut-2'(Z)-enyl)malonate 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以97%的产率得到(Z)-dimethyl 2-(4-hydroxybut-2-en-1-yl)malonate
  参考文献：
  名称：

  Synthesis of Carba Analogues of 2'-Deoxy-4'-C-(hydroxymethyl)nucleosides

  摘要：

  通过将胸腺嘧啶和腺嘌呤的钠盐分别加入二甲基（Z）-（4-氧代丁-2-烯-1-基）丙二酸二甲酯（1），制备了拉氏二甲基2-羟基-4-[5-甲基-2（1H），4（3H）-二氧代嘧啶-1-基]-（7a和8a）和二甲基4-（6-氨基嘌呤-9-基）-2-羟基环戊烷-1,1-二羧酸二甲酯（7b和8b）。在甲醇中加入硼氢化钠和硫酸，将二酯还原，得到相应的拉氏2,2-双（羟甲基）-4-[5-甲基-2（1H），4（3H）-二氧代嘧啶-1-基]-（14a和15a）、4-(6-氨基嘌呤-9-基)-2,2-双（羟甲基）环戊烷-1-醇（14b和15b）、甲基（±）-顺式-2-羟基-1-羟甲基-4-[5-甲基-2（1H），4（3H）-二氧代嘧啶-1-基]-（13a）和甲基（±）-顺式-4-(6-氨基嘌呤-9-基)-2-羟基-1-羟甲基环戊烷-1-羧酸酯（13b）。

  DOI：

  10.1135/cccc19991485
• 作为产物：
  描述：

  (Z)-4-bromo-2-butenyl acetate 、 丙二酸二甲酯 在 sodium hydride 作用下， 生成 dimethyl 2-(4'-acetoxybut-2'(Z)-enyl)malonate
  参考文献：
  名称：

  Palladium-Catalyzed Intramolecular Metallo-Ene Reactions Using Allylic Sulfones as Enophiles.

  摘要：

  研究了使用烯丙基砜作为亲电试剂的钯催化的分子内金属烯反应。在80°C的乙酸中，进行了在适当位置带有烯丙基砜的烯丙基乙酸酯和甲基碳酸酯的钯催化反应，得到了具有极高非对映选择性的环化产物，即环己烷衍生物。通过使用几种模型化合物在不同反应条件下考察了这些反应的立体化学特性。

  DOI：

  10.1248/cpb.42.786

文献信息

• Palladium-Catalyzed Bicyclization of 2-Bromo-1,6-dienes and -1,6-enynes to 5-Membered-Ring-Annelated Vinylcyclopropane Derivatives
  作者：Arno G. Steinig、Armin de Meijere

  DOI：10.1002/(sici)1099-0690(199906)1999:6<1333::aid-ejoc1333>3.0.co;2-g

  日期：1999.6

  can be regarded as a dehydrodimer of the vinylcyclopropane 35. The presumption that the formation of 63 involves the alkenylpalladium species 65 was supported by its successful inter- as well as intramolecular trapping with formate as a hydride source to yield the vinylcyclopropane 35. The reaction pathways leading to the vinylcyclopropane derivatives 35 and 63 have in common that an alkylpalladium species

  钯催化的 2-溴-1,6-二烯 6 与溴烯基部分上的乙酰氧基甲基取代基的环化不仅产生预期的 1-乙酰氧基甲基-1,3-二烯 40，而且产生双环乙烯基环丙烷 35， 1,3-二烯 36 和三烯 37（树枝状烯）。所有这些化合物均由 2-溴-1,6-二烯的初始 5-exo-trig 环化产生。By proper choice of the reaction conditions (ligand, base, allylic leaving group) each of these compounds could be formed selectively. 少量 (3–5%) 的异构化 1-乙酰氧基甲基-1,3-二烯 38 和 6-内产物 39 也被分离出来。由于烯基部分（化合物27）上的乙酰氧基甲基取代基，仅形成1,4-二烯44。在三键上具有甲氧基羰基氧基亚甲基取代基的相关 1,6-烯炔 57
• Palladium(O)-catalyzed allylic alkylation and amination of allylic phosphates
  作者：Yoshio Tanigawa、Kazuaki Nishimura、Akihiko Kawasaki、Shun-Ichi Murahashi

  DOI：10.1016/s0040-4039(00)85891-8

  日期：1982.1

  Allyl diethyl phosphates (1) can be easily substituted with malonates and amines in the presence of palladium(O) catalyst. Synthetic utility of the reaction is demonstrated by the sequential amination-amination and alkylation-amination of (Z)-4-acetoxybut-2-enyl diethyl phosphate (1b) with high regio- and stereoselectivity.

  在钯（O）催化剂的存在下，磷酸烯丙基二乙酯（1）可以很容易地被丙二酸酯和胺取代。通过具有高区域和立体选择性的（Z）-4-乙酰氧基丁-2-烯基二乙基磷酸二乙酯（1b）的顺序胺化胺化和烷基化胺化，证明了该反应的合成效用。
• TFA-mediated intramolecular Friedel–Crafts reaction. An efficient metal and halogen free route to stereoselective synthesis of benzocycles
  作者：Shengming Ma、Junliang Zhang

  DOI：10.1016/s0040-4020(03)01026-3

  日期：2003.8

  6-Acetoxy-4-alkenyl arenes undergo regio- and stereoselective intramolecular Friedel-Crafts reaction affording benzocycles in moderate to excellent yields in TFA/HOAc (3: 1). It was observed that introduction of alkyls or phenyl group to the allylic acetate moiety facilitates the cyclization reaction. The optically active tricyclic (4bR,8aS)-4b,7,8,8a,9,10-hexahydrophenanthrene skeleton could also be easily obtained in excellent yields. (C) 2003 Elsevier Ltd. All rights reserved.
• Diastereoselective cycloisomerizations of enediynes via palladium catalysis
  作者：Barry M. Trost、Yian Shi

  DOI：10.1021/ja00079a033

  日期：1993.12

  Considerations of atom economy drive a search for reactions that are simple additions which, performed intramolecularly, are cycloisomerizations. Exposure of acyclic enediynes to a catalyst generated by mixing a Pd(O) complex with acetic acid normally in the presence of a phosphine ligand creates [5.6.51 and [6.6.51 tricycles with extraordinary diastereoselectivity of remote stereogenic centers. Effects of substituents on the tethers as well as the olefinic and acetylenic bonds reveal a wide tolerance of functionality. While geminal substitution facilitates the cycloisomerization, it is not required. Allylic oxygen plays a role as a regioselectivity control element. Cycloisomerization dominates over allylic ionization in such cases by proper tuning of the ligand. The mechanism of this reaction appears to vary depending upon the structure of the substrate. In the normal cases, the process involves three stages, initiation, propagation, and termination. Chemoselective initiation at the acetylenic linkage closest to one of the chain's termini occurs by hydropalladation. Propagation entails intramolecular carbametalations. Termination by beta-hydrogen elimination generates a hexatriene that undergoes high rotoselectivity in its disrotatory cyclization to generate the final product. Blocking formation of the hexatriene shuts down reaction. With substrates bearing a gamma-siloxypropiolate as the acetylenic initiator, cycloisomerization forms a tricycle with different positions of the double bonds. In contrast' to the case of the other substrates, blocking formation of a hexatriene does not shut down cycloisomerization. Invoking a novel intramolecular Diels-Alder reaction of a dienylpalladium intermediate derived from the diyne moiety with the olefin, likely assisted by coordination to palladium, accounts for our observations. The ease of availability of the acyclic substrates because of the versatility of the acetylenes combined with the high chemo-, regio-, and diastereoselectivity makes this atom-economical reaction a very practical approach for the construction of polycycles.
• Kumareswaran; Pachamuthu; Vankar, Synlett, 2000, # 11, p. 1652 - 1654
  作者：Kumareswaran、Pachamuthu、Vankar

  DOI：——

  日期：——