5-methylbicyclo<2.2.1>hept-5-en-2-one | 22405-40-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-methylbicyclo<2.2.1>hept-5-en-2-one
• 英文别名: 5-Methylbicyclo<2.2.1>hept-5-en-2-on；5-Methyl-norbornen-(5)-on-(2)；5-Methyl-norbornen-5-on-(2)；5-Methyl-norborn-5-en-2-on；5-Methyl-2-norbornenon；5-Methyl-norbornenon；5-Methylbicyclo[2.2.1]hept-5-en-2-one
• CAS: 22405-40-9
• 化学式: C₈H₁₀O
• 分子量: 122.167
• InChiKey: FXRQSPWCDUCCOA-UHFFFAOYSA-N

物化性质

• 沸点：
  195.2±9.0 °C(Predicted)
• 密度：
  1.081±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  5-methylbicyclo<2.2.1>hept-5-en-2-one 生成 2-Phenyl-5-methyl-exo-norbornenol
  参考文献：
  名称：

  Structural effects in solvolytic reactions. XII. Solvolysis of 2-aryl-5-methyl- and 2,5-dimethyl-2-norbornenyl p-nitrobenzoates. Evidence for major .pi. participation revealed by the tool of increasing electron demand

  摘要：

  DOI：

  10.1021/ja00859a011
• 作为产物：
  描述：

  甲基环戊二烯 、 乙酸乙烯酯 以29%的产率得到
  参考文献：
  名称：

  SALOMON, ROBERT G.;SACHINVALA, NAVZER D.;ROY, SUBHAS;BASU, BASUDEB;RAYCHA+, J. AMER. CHEM. SOC., 113,(1991) N, C. 3085-3095

  摘要：

  DOI：

文献信息

• Gasphasen-Thermolyse Methyl-substituierter Bicyclo[3.2.0]hept-2-en-7-one
  作者：Peter Schiess、Peter Fünfschilling

  DOI：10.1002/hlca.19760590533

  日期：1976.7.14

  Gas phase thermolysis of methyl-bicyclo [3.2.0] hept-2-en-7-ones.

  甲基-双环[3.2.0]庚-2-烯-7-酮的气相热解。
• Total synthesis of spatane diterpenes: the tricyclic nucleus
  作者：Robert G. Salomon、Navzer D. Sachinvala、Subhas Roy、Basudeb Basu、Swadesh R. Raychaudhuri、Donald B. Miller、Ram B. Sharma

  DOI：10.1021/ja00008a043

  日期：1991.4

  A convergent, stereocontrolled construction of the cis,anti,cis-tricyclo[5.3.0.0(2,6)]decane nucleus of spatane diterpenes was achieved by 2-pi + 2-pi photocycloaddition of 2-cyclopenten-1-one, as an A-ring precursor, with a carbonyl-masked derivative of 6-methylbicyclo[2.2.1]hept-5-en-2-one as a temporarily bridged C-ring precursor. By design, the temporary bridge assures the correct stereochemical relationship between the B-ring stereocenters and the C-ring hydroxyl substituent that is present in latent form in the oxoethano bridge. Serendipitously, the bridge also fosters a favorable orientation of the photocycloaddition that contrasts with the nonselective 2-pi + 2-pi-photocycloadditions of unbridged 1-methylcyclopentenes with 2-cyclopenten-1-one. Wittig methylenation of the A-ring carbonyl in photoproduct 24 followed by hydrolysis to 25 and catalytic hydrogenation introduces a methyl group at position 1 with a 10:1 preference for the requisite stereochemistry in 26. Even higher stereoselectivity was achieved by SO2-promoted isomerization of the exocyclic C=C bond in 25 to an endocyclic disposition in 29 prior to catalytic hydrogenation. Johnson's sulfoximine method is especially effective for resolution of ketone 29. The oxoethano bridge in ketone 26n is oxidized rapidly but nonregioselectively by an H2SO4-catalyzed reaction with peracetic acid, producing a 57:43 mixture of 14 and 34. Regioselective generation of the desired lactone 14 could be accomplished by a much slower oxidation with peracetic acid and no added H2SO4. The necessary configuration at position 7 in 49 was generated stereoselectively by a novel homoallylic hydroxyl-directed, pseudointramolecular delivery of hydride to the methylenemalonic ester in the precursor 48. Conversion of the malonic ester moiety in 49 into an allylic alcohol was accomplished in 92% overall yield by monosaponification, decarboxylative condensation with formaldehyde and reduction of the resulting acrylic ester with i-Bu2AlH. Selective oxidation of the allylic hydroxyl followed by acetylation delivered acetate (+)-11a, which is identical with an oxidative degradation product from spatane diterpenes.
• Kirmse, Wolfgang; Hartmann, Marianne; Siegfried, Rainer, Chemische Berichte, 1981, vol. 114, # 5, p. 1793 - 1808
  作者：Kirmse, Wolfgang、Hartmann, Marianne、Siegfried, Rainer、Wroblowsky, Heinz-Juergen、Zang, Brigitte、Zellmer, Volker

  DOI：——

  日期：——
• Buchbauer, Gerhard; Rohner, Helga Christiane, Liebigs Annalen der Chemie, 1981, # 11, p. 2093 - 2095
  作者：Buchbauer, Gerhard、Rohner, Helga Christiane

  DOI：——

  日期：——
• The protonated cyclopropane route to bicyclic cations
  作者：Wolfgang Kirmse、Joachim Streu

  DOI：10.1021/jo00380a007

  日期：1987.2