cis-3-ethoxycarbonyloxy-5-carbomethoxy-1-cyclohexene | 144681-41-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机碳酸及其衍生物
• 英文名称: cis-3-ethoxycarbonyloxy-5-carbomethoxy-1-cyclohexene
• 英文别名: methyl cis-<5-(ethoxycarbonyl)oxy-3-cyclohexene-1-carboxylate>；methyl cis-5-(ethoxycarbonyloxy)-3-cyclohexene-1-carboxylate；methyl (1R,5R)-5-ethoxycarbonyloxycyclohex-3-ene-1-carboxylate
• CAS: 144681-41-4
• 化学式: C₁₁H₁₆O₅
• 分子量: 228.245
• InChiKey: QGZDEKNIVSJSKJ-BDAKNGLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  cis-3-ethoxycarbonyloxy-5-carbomethoxy-1-cyclohexene 在 正丁基锂 、 (1,1'-双(二苯基膦)二茂铁)二氯化镍 、 硼酸三甲酯 、 sodium methylate 、 potassium iodide 作用下， 以 甲醇 为溶剂， 生成
  参考文献：
  名称：

  Nickel-catalysed substitution reactions of allylic carbonates with aryl- and alkenyl-borates

  摘要：

  1,3-二取代的烯丙基碳酸酯 3 与芳基和烯基硼酸盐 4 的取代反应在 [NiCl2(dppf)] 的催化下进行，其中 dppf = 1,1′-双(二苯基膦)铁烯， 在环状碳酸酯 7 的情况下，该反应完全反转进行。

  DOI：

  10.1039/c39940001789
• 作为产物：
  描述：

  氯甲酸乙酯 、 cis-methyl 5-hydroxycyclohex-3-enecarboxylate 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 乙醚 为溶剂， 反应 24.0h， 以90%的产率得到cis-3-ethoxycarbonyloxy-5-carbomethoxy-1-cyclohexene
  参考文献：
  名称：

  钯（O）催化的硫醇烷基化

  摘要：

  钯（O）通过芳族硫醇催化的各种烯丙基碳酸酯的烷基化反应，可以很容易地以很高的收率容易地制备各种烯丙基芳基硫化物。无论反应温度如何，该反应在π-烯丙基系统的受阻较弱的一侧具有区域选择性和取代性，并且是非对映选择性的，并且净保留构型。

  DOI：

  10.1016/s0040-4020(01)81764-6

文献信息

• Stereochemistry of the palladium-catalyzed allylic substitution: the syn-anti dichotomy in the formation of (π-allyl)palladium complexes and their equilibration
  作者：Ivo Starý、Jaroslav Zajíček、Pavel Kočovský

  DOI：10.1016/s0040-4020(01)88263-6

  日期：1992.1

  The mechanism of palladium(0)-catalyzed allylic substitution has been investigated with the aim of finding whether or not the intermediate (π-allyl)palladium complexes can arise in a syn fashion as an alternative to the well known anti-mechanism. Using (diphenylphosphino)acetate as a leaving group and stereochemically biased substrates 30b and 35b evidence for the syn stereochemistry has been acquired

  已经研究了钯（0）催化的烯丙基取代的机理，目的是发现中间（π-烯丙基）钯配合物是否可以以合成方式替代众所周知的抗机理而出现。使用（二苯基膦基）乙酸酯作为离去基团和立体化学偏向的底物30b和35b，已经获得了用于顺式立体化学的证据（30b → 31和35b → 36）。起始烯丙基酯中的严重空间拥塞促进了立体化学的这种逆转（这损害了普通的抗-机制），并通过Pd（0）试剂与离去基团的预配位得到增强。后者的作用显然降低了活化熵。与环己烯衍生物10b的，18B，和19B和无环衬底25b中，其中的空间位阻不操作，该抗-mechanism产生η 3 -complexes占优势甚至对于（二苯基膦基）乙酸盐。在升高的温度下，η快速平衡3 -complexes（13 ⇄ 14和20 ⇄ 21在与亲核试剂反应之前已观察到）。该作用归因于作为钯的配体的（二苯基膦基）乙酸根离子的存在。
• Nickel-Catalyzed Coupling Reaction of 1,3-Disubstituted Secondary Allylic Carbonates and Lithium Aryl- and Alkenylborates
  作者：Yuichi Kobayashi、Ryo Mizojiri、Eitatsu Ikeda

  DOI：10.1021/jo960458c

  日期：1996.1.1

  This account describes coupling reaction of 1,3-disubstituted secondary allylic carbonates with lithium aryl- and alkenylborates in the presence of a nickel. catalyst. Berates examined are 4, 5, and 6, and reactivity and selectivity were investigated using the allylic carbonates la and Ib. Coupling of la,b with berates 4 was effected with the nickel catalyst, NiCl2(PPh(3))(2) or NiCl2(dppf), in THF at 45-65 degrees C to provide products 3 in good yields with almost 100% regio- and stereoselectivities. Trivalent organoboranes prepared from acetylenes by hydroboration with catecholborane also underwent coupling reaction with la,b after transformation to berates 5 with MeLi. Though coupling using 4 and 5 required elevated temperature (45-65 degrees C), cyclic berates 6 prepared in situ from boronates 8 and MeLi were found to couple with la,b at room temperature or below. Regio- and stereoselectivities were almost 100% as were observed in the cases of 4 and 5. In these reactions, palladium complexes such as Pd(PPh(3))(4), Pd-2(dba)(3) . CHCl3 + 2 PPh(3) showed no catalytic activity. Stereochemical aspect of the present reaction was studied using cyclohexenyl carbonate 24 with 2-furylborate 4e and phenylborate 6a, and was found to proceed with overall anti fashion. With additional experiments, the mechanism of the present reaction was discussed in terms of transient pi-allylnickel intermediates.
• Kobayashi Yuichi, Ikeda Eitatsu, J. Chem. Soc. Chem. Commun, (1994) N 15, S 1789- 1790
  作者：Kobayashi Yuichi, Ikeda Eitatsu

  DOI：——

  日期：——

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