Ethyl 2-cyclopentylprop-2-enoate | 81143-91-1

• 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: Ethyl 2-cyclopentylprop-2-enoate
• 英文别名: ethyl 2-cyclopentylacrylate；Ethyl2-cyclopentylprop-2-enoate
• CAS: 81143-91-1
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: VPQZBEBHNCEGMY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Ethyl 2-cyclopentylprop-2-enoate 在 manganese(IV) oxide 、 二异丁基氢化铝 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 101.0h， 生成 2-cyclopentylacrylaldehyde
  参考文献：
  名称：

  Total synthesis of spatol and other spatane diterpenes

  摘要：

  Total syntheses of three spatane diterpenes stoechospermol (1), 5(R),15(R),18-trihydroxyspata-13,16(E)-diene (2), and (+)-spatol (3) were accomplished from a common intermediate, diol 7. The total synthesis established as R the absolute configuration at the 15-position in 2. Novel stereospecific transformations of 2,3-epoxy-1,4-diols into vicinal diepoxides were demonstrated and exploited for assembling the sensitive allylic diepoxide in the side chain of spatol. This new synthetic method allows the conversion of both 1,2-threo-2,3-trans- and 1,2-erythro-2,3-trans-2,3-epoxy-1,4-diols into vicinal 1,2-cis-2,3-erythro-1,3-diepoxides. Unexpected stability toward hydroxide anion was found for the allylic diepoxide functional array. This observation provides presumptive evidence that acid catalysis is operative in the epoxide cleaving substitution reaction of spatol by the weakly nucleophilic chloride anion that gives chlorohydrin 4. A proclivity for erythro-selective epoxidation of allylic silyl ethers was found. The utility of C-silyl substituents for reversing this stereoselectivity, i.e., favoring threo-selective epoxidation of allylic silyl ethers, was established.

  DOI：

  10.1021/ja00008a044
• 作为产物：
  描述：

  环戊基丙二酸二乙酯 在 氢氧化钾 、 聚合甲醛 、 sodium acetate 、 溶剂黄146 、 二乙胺 作用下， 以 乙醇 、 水 为溶剂， 反应 12.0h， 生成 Ethyl 2-cyclopentylprop-2-enoate
  参考文献：
  名称：

  Total synthesis of spatol and other spatane diterpenes

  摘要：

  Total syntheses of three spatane diterpenes stoechospermol (1), 5(R),15(R),18-trihydroxyspata-13,16(E)-diene (2), and (+)-spatol (3) were accomplished from a common intermediate, diol 7. The total synthesis established as R the absolute configuration at the 15-position in 2. Novel stereospecific transformations of 2,3-epoxy-1,4-diols into vicinal diepoxides were demonstrated and exploited for assembling the sensitive allylic diepoxide in the side chain of spatol. This new synthetic method allows the conversion of both 1,2-threo-2,3-trans- and 1,2-erythro-2,3-trans-2,3-epoxy-1,4-diols into vicinal 1,2-cis-2,3-erythro-1,3-diepoxides. Unexpected stability toward hydroxide anion was found for the allylic diepoxide functional array. This observation provides presumptive evidence that acid catalysis is operative in the epoxide cleaving substitution reaction of spatol by the weakly nucleophilic chloride anion that gives chlorohydrin 4. A proclivity for erythro-selective epoxidation of allylic silyl ethers was found. The utility of C-silyl substituents for reversing this stereoselectivity, i.e., favoring threo-selective epoxidation of allylic silyl ethers, was established.

  DOI：

  10.1021/ja00008a044

文献信息

• Nitration of α,β-unsaturated esters. Evidence for positive charge build-up adjacent to carbonyl carbon
  作者：Stuart A. Hewlins、John A. Murphy、Jian Lin、David E. Hibbs、Michael B. Hursthouse

  DOI：10.1039/a607170h

  日期：——

  Reactive intermediates formed in the nitration of certain α,β-unsaturated esters with nitronium tetrafluoroborate exhibit behaviour expected of highly reactive α-carbonyl cations. Three diagnostic reaction types have been observed which indicate the presence of these destabilised cations: (i) trapping in a Ritter reaction, (ii) cyclopropane formation from propyl cations, (iii) Wagner–Meerwein migration of alkyl groups. Semi-empirical calculations of the relative gas-phase stabilities of the proposed intermediate cations are useful in rationalising the observed chemistry.

  在用四氟硼酸亚硝酰进行某些α,β-不饱和酯的硝化反应中形成的活性中间体表现出高度活性α-羰基阳离子的预期行为。已观察到三种诊断性的反应类型，表明这些不稳定的阳离子的存在：（i）在Ritter反应中捕获，（ii）从丙基阳离子形成环丙烷，（iii）烷基的Wagner-Meerwein迁移。对所提出的中间阳离子的相对气相稳定性的半经验计算有助于合理化观察到的化学现象。
• Efficient synthesis of chiral γ-aminobutyric esters <i>via</i> direct rhodium-catalysed enantioselective hydroaminomethylation of acrylates
  作者：Anton Cunillera、Miriam Díaz de los Bernardos、Martine Urrutigoïty、Carmen Claver、Aurora Ruiz、Cyril Godard

  DOI：10.1039/c9cy01797f

  日期：——

  The first successful rhodium catalysed asymmetric hydroaminomethylation of alkenes using a single catalyst is reported with ees up to 86%.

  首次成功地利用单一催化剂进行烯烃的铑催化不对称水胺甲基化反应，其对映选择性高达86%。
• Skeletal rearrangements in the nitrations of α,β-unsaturated esters
  作者：Stuart A Hewlins、John A Murphy、Jian Lin

  DOI：10.1016/0040-4039(95)00421-8

  日期：1995.4

  Reaction of α,β-unsaturated esters with nitronium tetrafluoroborate in acetonitrile at −16°C affords products of skeletal cationic rearrangements suggesting the intermediacy of highly reactive α-carbonyl cations.

  α，β-不饱和酯与四氟硼酸硝鎓在乙腈中于-16°C反应生成骨架阳离子重排产物，表明存在高反应性α-羰基阳离子。
• Stetter, Hermann; Marten, Klaus, Liebigs Annalen der Chemie, 1982, # 2, p. 240 - 249
  作者：Stetter, Hermann、Marten, Klaus

  DOI：——

  日期：——
• SALOMON, ROBERT G.;BASU, BASUDEB;ROY, SUBHAS;SACHINVALA, NAVZER D., J. AMER. CHEM. SOC., 113,(1991) N, C. 3096-3106
  作者：SALOMON, ROBERT G.、BASU, BASUDEB、ROY, SUBHAS、SACHINVALA, NAVZER D.

  DOI：——

  日期：——