cis-dimethyl cyclohex-4-ene-1,3-dicarboxylate | 71195-23-8

• 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: cis-dimethyl cyclohex-4-ene-1,3-dicarboxylate
• 英文别名: cis-5-methoxycarbonyl-2-cyclohexenyl acetate；Dimethyl (1S,3S)-cyclohex-4-ene-1,3-dicarboxylate；dimethyl (1S,3S)-cyclohex-4-ene-1,3-dicarboxylate
• CAS: 71195-23-8
• 化学式: C₁₀H₁₄O₄
• 分子量: 198.219
• InChiKey: FMEGVOCGASPFSX-SFYZADRCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  cis-dimethyl cyclohex-4-ene-1,3-dicarboxylate 生成 顺-1,3-环己烷二甲酸
  参考文献：
  名称：

  Palladium(II)-catalyzed carboxylation reactions of olefins: scope and utility

  摘要：

  DOI：

  10.1021/jo01334a006
• 作为产物：
  描述：

  甲醇 、 一氧化碳 、 trans-diethyl 5-(methoxycarbonyl)-2-cyclohexen-1-yl phosphate 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex N,N-二异丙基乙胺 、 三苯基膦 作用下， 50.0 ℃ 、6.08 MPa 条件下， 以73%的产率得到cis-dimethyl cyclohex-4-ene-1,3-dicarboxylate
  参考文献：
  名称：

  Palladium(0)-catalyzed alkoxycarbonylation of allyl phosphates and acetates

  摘要：

  Palladium-catalyzed alkoxycarbonylation of allyl phosphates under CO (1 atm) at 50-degrees-C proceeds highly efficiently to give the corresponding beta,gamma-unsaturated esters. The carbonylation of geranyl phosphate ((E)-11) under CO (1 atm) at 50-degrees-C gave ethyl ester of homogeranic acid ((E)-12) stereoselectively. The carbonylation takes place at the least substituted allylic positions with inversion of configuration. Typically, the methoxycarbonylation of cis-5-(methoxycarbonyl)-2-cyclohexen-1-yl phosphate (cis-16) gave trans-dimethyl 2-cyclohexene-1,5-dicarboxylate (trans-17) selectively. Alkoxycarbonylation of allyl acetates is performed for the first time in the presence of a catalytic amount of bromide ion. The reaction can be rationalized by assuming the mechanism which involves oxidative addition of palladium(0) species to allyl acetates to give pi-allylpalladium acetate, fast ligand exchange of the acetate with bromide, insertion of carbon monoxide to give acylpalladium species, and alkoxylation.

  DOI：

  10.1021/jo00058a040

文献信息

• Palladium(0)-catalyzed carbonylation of allyl phosphates and allyl acetates. Selective synthesis of β,γ-unsaturated esters
  作者：Shun-Ichi Murahashi、Yasushi Imada、Yuki Taniguchi、Shin-ya Higashiura

  DOI：10.1016/s0040-4039(00)80648-6

  日期：1988.1

  Palladium catalyzed carbonylations of allyl phosphates and allyl acetates give β,γ-unsaturated esters efficiently. The latter reaction requires bromide ion as a co-catalyst.

  钯催化的烯丙基磷酸酯和乙酸烯丙酯的羰基化反应可有效地生成β，γ-不饱和酯。后一反应需要溴离子作为助催化剂。
• Palladium-catalyzed asymmetric allylic alkylation with an indenide
  作者：Tamio Hayashi、Toshimasa Suzuka、Atsushi Okada、Motoi Kawatsura

  DOI：10.1016/j.tetasy.2003.11.028

  日期：2004.2

  synthesis of a chiral indene (97% ee) was realized by asymmetric allylic substitution of 1,3-diphenyl-2-propenyl acetate with an indenide generated from indene and cesium carbonate in the presence of a palladium catalyst coordinated with (S)-Ph-phox. The stereochemistry of the allylic substitution with the indenide was demonstrated to be net retention.

  在（S）配位的钯催化剂的存在下，用茚和碳酸铯生成的茚酸酯进行1，对称的1,3-二苯-2-丙烯乙酸乙烯酯的不对称烯丙基取代，催化了手性茚（97％ee）的催化合成。-Ph-phox。用茚化物进行的烯丙基取代的立体化学被证明是净保留。
• Palladium(II)-catalyzed carboxylation reactions of olefins: scope and utility
  作者：J. K. Stille、R. Divakaruni

  DOI：10.1021/jo01334a006

  日期：1979.9
• Palladium(0)-catalyzed alkoxycarbonylation of allyl phosphates and acetates
  作者：Shunichi Murahashi、Yasushi Imada、Yuki Taniguchi、Shinya Higashiura

  DOI：10.1021/jo00058a040

  日期：1993.3

  Palladium-catalyzed alkoxycarbonylation of allyl phosphates under CO (1 atm) at 50-degrees-C proceeds highly efficiently to give the corresponding beta,gamma-unsaturated esters. The carbonylation of geranyl phosphate ((E)-11) under CO (1 atm) at 50-degrees-C gave ethyl ester of homogeranic acid ((E)-12) stereoselectively. The carbonylation takes place at the least substituted allylic positions with inversion of configuration. Typically, the methoxycarbonylation of cis-5-(methoxycarbonyl)-2-cyclohexen-1-yl phosphate (cis-16) gave trans-dimethyl 2-cyclohexene-1,5-dicarboxylate (trans-17) selectively. Alkoxycarbonylation of allyl acetates is performed for the first time in the presence of a catalytic amount of bromide ion. The reaction can be rationalized by assuming the mechanism which involves oxidative addition of palladium(0) species to allyl acetates to give pi-allylpalladium acetate, fast ligand exchange of the acetate with bromide, insertion of carbon monoxide to give acylpalladium species, and alkoxylation.