dimethyl (E)-(5-carbomethoxy-1-cyclohexen-3-yl)malonate | 74545-66-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: dimethyl (E)-(5-carbomethoxy-1-cyclohexen-3-yl)malonate
• 英文别名: methyl trans-α,5-dimethoxycarbonyl-3-cyclohex-1-eneacetate；methyl trans-6-(bis(methoxycarbonyl)methyl)cyclohexen-4-carboxylate；dimethyl (5-carbomethoxy-1-cyclohexen-3-yl)malonate；dimethyl 2-[(1S,5R)-5-methoxycarbonylcyclohex-2-en-1-yl]propanedioate
• CAS: 74545-66-7
• 化学式: C₁₃H₁₈O₆
• 分子量: 270.282
• InChiKey: MMJITTDFLXSCJB-RKDXNWHRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 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 (E)-(5-carbomethoxy-1-cyclohexen-3-yl)malonate 在 四甲基醋酸铵 作用下， 以 六甲基磷酰三胺 为溶剂， 反应 20.0h， 以75%的产率得到2-Cyclohexene-1-acetic acid, 5-(methoxycarbonyl)-, methyl ester
  参考文献：
  名称：

  Allylic alkylation. Palladium-catalyzed substitutions of allylic carboxylates. Stereo- and regiochemistry

  摘要：

  DOI：

  10.1021/ja00534a029
• 作为产物：
  描述：

  6-氧杂双环[3.2.1]辛-3-烯-7-酮 在 四(三苯基膦)钯 吡啶 、 sodium methylate 、 三苯基膦 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 34.42h， 生成 dimethyl (E)-(5-carbomethoxy-1-cyclohexen-3-yl)malonate
  参考文献：
  名称：

  Allylic alkylation. Palladium-catalyzed substitutions of allylic carboxylates. Stereo- and regiochemistry

  摘要：

  DOI：

  10.1021/ja00534a029

文献信息

• Molybdenum catalysts for allylic alkylation
  作者：Barry M. Trost、Mark Lautens

  DOI：10.1021/ja00384a071

  日期：1982.10

  This paper reports on the stoichiometric and catalytic allylic substituion reactions involving molybdenum complexes and the sensitivity of regioselectivity toward the nature of the ligands on molybdenum. Results indicated that the allylic alkylation catalyzed by molybdenum forms a useful and frequently complementary alternative to the palladium-catalyzed reaction. For example, regioselectivity appears

  本文报道了涉及钼配合物的化学计量和催化烯丙基取代反应以及区域选择性对钼配体性质的敏感性。结果表明，由钼催化的烯丙基烷基化形成了钯催化反应的有用且经常互补的替代方案。例如，在 Mo 的情况下，区域选择性似乎对配体变化更敏感。在 ..pi..-allyl 片段的一级碳和二级碳上的连接选择性更高。存在。另一方面，这些反应需要更高的温度和更长的时间。需要对这种钼化学进行更彻底的评估，以描绘其全部潜力。
• Palladium-Catalyzed Reactions of Allylic Boronic Esters with Nucleophiles: Novel Umpolung Reactivity
  作者：Varinder Aggarwal、Phillip Unsworth、Lorenz Löffler、Adam Noble

  DOI：10.1055/s-0034-1380869

  日期：——

  Oxidative palladium-catalyzed reaction conditions have been developed to allow for regioselective and stereoselective coupling of allylic boronic esters with a range of carbon-, oxygen-, and nitrogen-based nucleophiles. Studies into the mechanism of the reaction have shown that the key transmetalation step occurs with retention of stereochemistry, since overall inversion is observed.

  已经开发出氧化钯催化的反应条件以允许烯丙基硼酸酯与一系列碳基、氧基和氮基亲核试剂的区域选择性和立体选择性偶联。对反应机理的研究表明，关键的金属转移步骤伴随着立体化学的保留而发生，因为观察到了整体反转。
• Palladium-Catalyzed Substitution of Allylic Fluorides
  作者：Amaruka Hazari、Véronique Gouverneur、John M. Brown

  DOI：10.1002/anie.200804310

  日期：2009.2.2

  As unusual substrates for the Tsuji–Trost allylation reaction, allylic fluorides are responsive to palladium‐catalyzed substitution. Their activity towards this reaction fits in the series OCO2Me>OBz≫F≫OAc. The classic stereoretention mechanism that involves sequential inversions does not operate in this case. Several distinct cases are considered.

  作为Tsuji–Trost烯丙基化反应的不常见底物，烯丙基氟化物对钯催化的取代反应敏感。它们对该反应的活性符合OCO 2 Me> OBz≫ F ≫OAc系列。在这种情况下，涉及顺序倒置的经典立体保留机制不起作用。考虑了几种不同的情况。
• Allyl sulfones as synthons for 1,1- and 1,3-dipoles via organopalladium chemistry
  作者：Barry M. Trost、Norman R. Schmuff、Michael J. Miller

  DOI：10.1021/ja00538a079

  日期：1980.8
• New homochiral phosphine ligands having a hexahydro-1H-pyrrolo[1,2-c]imidazolone backbone: preparation and use for palladium-catalyzed asymmetric alkylation of cycloalkenyl carbonates
  作者：Kazutaka Shibatomi、Yasuhiro Uozumi

  DOI：10.1016/s0957-4166(02)00467-6

  日期：2002.8

  New chiral ligands having a pyrrolo[1,2-c]imidazolone backbone were prepared by condensation of anilides of homochiral cyclic amino acids with 2-(diphenylphosphino)benzaldehyde. Of these ligands, (3R,9aS)-(3-(2-diphenylphosphino)phenyl-2-phenyl)tetrahydro-1H-imidazo[1,5-a]indole-1-one was found to be effective for palladium-catalyzed asymmetric allylic alkylation of cycloalkenyl carbonates with dimethyl malonate to give the corresponding dimethyl cycloalkenylmalonates with e.e. of up to 89%. (C) 2002 Elsevier Science Ltd. All rights reserved.