2-Ethynyl-2-methyl-2,3,4,5,6,7-hexahydrobenzofuran-4-one | 139722-21-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并呋喃
• 英文名称: 2-Ethynyl-2-methyl-2,3,4,5,6,7-hexahydrobenzofuran-4-one
• 英文别名: 2-Ethynyl-2-methyl-3,5,6,7-tetrahydro-benzofuran-4-one；2-ethynyl-2-methyl-3,5,6,7-tetrahydro-1-benzofuran-4-one
• CAS: 139722-21-7
• 化学式: C₁₁H₁₂O₂
• 分子量: 176.215
• InChiKey: YFCREOSKKANNGJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  isopropenylacetylene, dicobalt-hexacarbonyl complex 、 1,3-环己二酮 在 copper diacetate 、 manganese triacetate 作用下， 以 溶剂黄146 为溶剂， 生成 2-Ethynyl-2-methyl-2,3,4,5,6,7-hexahydrobenzofuran-4-one
  参考文献：
  名称：

  μ-[3-4-η-(1-Alken-3-yne)hexacarbonyldicobalt complexes: Radical cyclocondensation mediated by manganese(III) acetate

  摘要：

  A regioselective pathway for the radical reaction of 1-alken-3-ynes with beta-dicarbonyl compounds, mediated by Mn(OAc)3, can be achieved by protection of the substrate triple bond with a hexacarbonyldicobalt moiety. Dihydrofuran and hexahydrobenzofuran derivatives are formed by intermolecular oxidative cyclization of intermediate cobalt-complexed propargyl radicals.

  DOI：

  10.1016/0022-328x(92)83037-i

文献信息

• Cobalt cluster-directed, manganese(III)-mediated chemo- and stereoselective radical reactions of 1-alken-3-ynes
  作者：Gagik G. Melikyan、Otto Vostrowsky、Walter Bauer、Hans Jurgen Bestmann、Masood Khan、Kenneth M. Nicholas

  DOI：10.1021/jo00080a036

  日期：1994.1

  A new strategy has been developed to effect selective Mn(OAc)(3)-mediated oxidative cycloaddition reactions of 1-alken-3-ynes with beta-dicarbonyl compounds. The three-step sequence involves (1) protection of the triple bond of the substrate with the -Co-2(CO)(6) group, (2) Mn-promoted radical addition of the beta-dicarbonyl compounds with the complexed enyne, and (3) oxidative demetalation. Mono-, di-, and tricycles, containing 2,3-dihydrofuran and tetrahydrofuran rings, are produced by exclusive attack on the uncomplexed C=C in moderate overall yields; formation of bi- and tricyclic derivatives occurs with excellent cis-stereoselectivity. Molecular mechanics calculations indicate that the cis ring fusion in these systems is thermodynamically favored. Reactions of the Co-complexed substrates proceed with Mn(III) promotion alone, whereas the free enynes require combined Mn(III)/Cu(II) mediation to produce furan derivatives, apparently reflecting the relative ease of oxidation of the respective intermediate radicals to carbocations. For the complexed substrates direct experimental proof for the formation of free carbocations along the reaction coordinate has been obtained by methanol trapping.