Ethyl 1-methyl-6-oxocyclohex-3-ene-1-carboxylate | 134906-27-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Ethyl 1-methyl-6-oxocyclohex-3-ene-1-carboxylate
• CAS: 134906-27-7
• 化学式: C₁₀H₁₄O₃
• 分子量: 182.219
• InChiKey: NZZSNGAVOWVZKJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2-(tert-butyldimethylsilyloxy)-1-methylcyclohexa-2,4-dienecarboxylic acid ethyl ester 以 四氢呋喃 为溶剂， 生成 Ethyl 1-methyl-6-oxocyclohex-3-ene-1-carboxylate
  参考文献：
  名称：

  过渡金属催化的烯醇醚与炔烃的反应：通过环丙基铂或金卡宾络合物，进行5-exo-dig与6-endo-dig环化反应。

  摘要：

  亲电子的Pt（II），Pd（II）和Au（III）氯化物以及Cu（I）络合物催化烯醇醚与炔烃在甲醇中的分子内反应，得到带有二甲基乙缩醛的五元或六元环。通过将烯醇醚和金属抗加成至炔烃中来进行反应。排除了亚乙烯基络合物在该反应中的可能参与。除了通常的5-exo-dig（或6-exo-dig）途径外，还发现某些烯炔还发生6-endo-dig途径。还发现了一种5-endo-dig环化的情况。提出了基于PtCl（2）和AuCl（3）配合物的DFT计算，包括外和内环化的过渡金属催化的炔烃烷氧基环化的一般方案。

  DOI：

  10.1002/chem.200204646

文献信息

• Solvent effects on manganese(III)-based oxidative free-radical cyclizations: ethanol and acetic acid
  作者：Barry B. Snider、John E. Merritt、Mark A. Dombroski、Brad O. Buckman

  DOI：10.1021/jo00019a014

  日期：1991.9

  Ethanol complements the typical solvent, acetic acid, for Mn(III)-based oxidative free-radical cyclizations. Cyclization of enol ether 1c to give gibberellic acid intermediate 6c is successful in ethanol, but not in acetic acid. Ethanol acts as a reducing agent for primary radicals, converting 13 and 33 to alkanes 17 and 32. Acetylenes can be used as substrates since the vinyl radicals 24 and 25 are reduced by ethanol to alkenes 26-28. The 1-hydroxyethyl radical obtained from ethanol is oxidized to acetaldehyde by Mn(III). The effect of solvent on the oxidative cyclization of unsaturated beta-keto esters 35 and 48 was examined. A higher percentage of 5-exo product is obtained in ethanol. The primary cyclopentanemethyl radicals 40 and 53 are oxidized mainly to alkenes 43 and 57 in ethanol and mainly to the alcohols 42 and 55 and lactones 41 and 58 in acetic acid.
• W(CO)₅·THF-Catalyzed Endo-Selective Cyclization of ω-Acetylenic Silyl Enol Ethers
  作者：Katsuya Maeyama、Nobuharu Iwasawa

  DOI：10.1021/ja973317g

  日期：1998.3.1
• Reaction of Enol Ethers with Alkynes Catalyzed by Transition Metals: 5exo-dig versus 6endo-dig Cyclizations via Cyclopropyl Platinum or Gold Carbene Complexes
  作者：Cristina Nevado、Diego J. Cárdenas、Antonio M. Echavarren

  DOI：10.1002/chem.200204646

  日期：2003.6.6

  in methanol is catalyzed by electrophilic Pt(II), Pd(II), and Au(III) chlorides and by a Cu(I) complex to give five- or six-membered rings bearing dimethyl acetals. The reaction takes place by an anti addition of the enol ether and the metal to the alkyne. The possible involvement of vinylidene complexes in this reaction is excluded. In addition to the usual 5-exo-dig (or 6-exo-dig) pathways, a 6-endo-dig

  亲电子的Pt（II），Pd（II）和Au（III）氯化物以及Cu（I）络合物催化烯醇醚与炔烃在甲醇中的分子内反应，得到带有二甲基乙缩醛的五元或六元环。通过将烯醇醚和金属抗加成至炔烃中来进行反应。排除了亚乙烯基络合物在该反应中的可能参与。除了通常的5-exo-dig（或6-exo-dig）途径外，还发现某些烯炔还发生6-endo-dig途径。还发现了一种5-endo-dig环化的情况。提出了基于PtCl（2）和AuCl（3）配合物的DFT计算，包括外和内环化的过渡金属催化的炔烃烷氧基环化的一般方案。