cis-2a-(Acetyloxy)-2,2a,4,8b-tetrahydro-1,1,2,2-tetramethylcyclobutaquinolin-3(1H)-one | 137792-96-2

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: cis-2a-(Acetyloxy)-2,2a,4,8b-tetrahydro-1,1,2,2-tetramethylcyclobutaquinolin-3(1H)-one
• 英文别名: cis-2a-(Acetyloxy)-2,2a,4,8b-tetrahydro-1,1,2,2-tetramethylcyclobuta[c]quinolin-3(1H)-one；(2aR,8bR)-1,1,2,2-tetramethyl-3-oxo-1,3,4,8b-tetrahydrocyclobuta[c]quinolin-2a(2H)-yl acetate
• CAS: 137792-96-2；1577157-31-3
• 化学式: C₁₇H₂₁NO₃
• 分子量: 287.359
• InChiKey: BJDAHRVKJLGPPT-GUYCJALGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.09
• 重原子数：
  21.0
• 可旋转键数：
  1.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  55.4
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  cis-2a-(Acetyloxy)-2,2a,4,8b-tetrahydro-1,1,2,2-tetramethylcyclobutaquinolin-3(1H)-one 在 水 、 碘 、 sodium hydride 、 potassium carbonate 、 mercury(II) oxide 作用下， 以 甲醇 、 苯 为溶剂， 反应 30.0h， 生成 1,2-Dihydro-1,1,2,2,5-pentamethylfuro<2,3-c>quinolin-4(5H)-one
  参考文献：
  名称：

  Photoinduced molecular transformations. 128. Regioselective [2 + 2] photocycloaddition of 3-acetoxyquinolin-2(1H)-one with alkenes and formation of furo[2,3-c]quinolin-4(5H)-ones, 1-benzazocine-2,3-diones, and cyclopropa[d]benz[1]azepine-2,3-diones via a .beta.-scission of cyclobutanoxyl radicals generated from the resulting [2 + 2] photoadducts

  摘要：

  We have found that [2 + 2]pi photoadducts can be obtained by the photoaddition of 3-acetoxyquinolin-2(1H)-one with acyclic and cyclic alkenes. The photoaddition of 3-acetoxy-2-quinolin-2(1H)-one with 2-methylpropene, 2,3-dimethyl-2-butene, and 2-methoxypropene thus afforded regioselective head-to-tail adducts in 59-97% yields. The photoaddition of 3-acetoxy-2-quinolin-2(1H)-one with cyclopentene and cyclohexene resulted in the formation of sterically disfavored cis-cisoid-cis photoadducts as the major products, with the accompanying formation of cis-transoid-cis photoadducts as the minor products in combined yields of 87 and 66%, respectively. The photolysis of the hypoiodites generated in situ from cyclobutanols derived from all of the photoadducts induced beta-scissions at the outer bonds of the corresponding cyclobutanoxyl radicals to give furo[2,3-c]quinolin-4(5H)-ones in 15-50% yields with an accompanying formation of 7- and 8-membered lactams arising from beta-scissions at the catacondensed bonds of the cyclobutanoxyl radicals in 2-62% yields. The molecular structure of one of the novel 7-membered lactams that successively fused with cyclopropane and cyclopentane rings was established to be trans-5,8,9,10,10a,10b-hexahydro-5-methylcyclopenta[3,4]cyclopropa[1,2-d]benzazepine-6,7-dione by X-ray crystallographic analysis. The pathways leading to the formation of all of these products arising from beta-scissions are discussed.

  DOI：

  10.1021/jo00028a037
• 作为产物：
  描述：

  3-羟基喹啉-2-酮 在 吡啶 作用下， 以 乙腈 为溶剂， 反应 27.25h， 生成 cis-2a-(Acetyloxy)-2,2a,4,8b-tetrahydro-1,1,2,2-tetramethylcyclobutaquinolin-3(1H)-one
  参考文献：
  名称：

  3-乙酰氧基喹诺酮的对映选择性分子间[2 + 2]光环加成反应：（-）-吡啶啉酮的全合成。

  摘要：

  通过对映选择性分子间[2 + 2]光环加成反应为关键步骤，通过简明的路线（六个步骤，总收率17％）从3-乙酰氧基喹诺酮合成了天然产物（-）-pinolinone。

  DOI：

  10.1039/c3cc49469a

文献信息

• Enantioselective, intermolecular [2+2] photocycloaddition reactions of 3-acetoxyquinolone: total synthesis of (−)-pinolinone
  作者：Florian Mayr、Christian Wiegand、Thorsten Bach

  DOI：10.1039/c3cc49469a

  日期：——

  The natural product (-)-pinolinone was synthesised via a concise route (six steps, 17% overall yield) from 3-acetoxyquinolone, employing an enantioselective intermolecular [2+2] photocycloaddition as the key step.

  通过对映选择性分子间[2 + 2]光环加成反应为关键步骤，通过简明的路线（六个步骤，总收率17％）从3-乙酰氧基喹诺酮合成了天然产物（-）-pinolinone。
• Photoinduced molecular transformations. 128. Regioselective [2 + 2] photocycloaddition of 3-acetoxyquinolin-2(1H)-one with alkenes and formation of furo[2,3-c]quinolin-4(5H)-ones, 1-benzazocine-2,3-diones, and cyclopropa[d]benz[1]azepine-2,3-diones via a .beta.-scission of cyclobutanoxyl radicals generated from the resulting [2 + 2] photoadducts
  作者：Kazuhiro Kobayashi、Masayoshi Suzuki、Hiroshi Suginome

  DOI：10.1021/jo00028a037

  日期：1992.1

  We have found that [2 + 2]pi photoadducts can be obtained by the photoaddition of 3-acetoxyquinolin-2(1H)-one with acyclic and cyclic alkenes. The photoaddition of 3-acetoxy-2-quinolin-2(1H)-one with 2-methylpropene, 2,3-dimethyl-2-butene, and 2-methoxypropene thus afforded regioselective head-to-tail adducts in 59-97% yields. The photoaddition of 3-acetoxy-2-quinolin-2(1H)-one with cyclopentene and cyclohexene resulted in the formation of sterically disfavored cis-cisoid-cis photoadducts as the major products, with the accompanying formation of cis-transoid-cis photoadducts as the minor products in combined yields of 87 and 66%, respectively. The photolysis of the hypoiodites generated in situ from cyclobutanols derived from all of the photoadducts induced beta-scissions at the outer bonds of the corresponding cyclobutanoxyl radicals to give furo[2,3-c]quinolin-4(5H)-ones in 15-50% yields with an accompanying formation of 7- and 8-membered lactams arising from beta-scissions at the catacondensed bonds of the cyclobutanoxyl radicals in 2-62% yields. The molecular structure of one of the novel 7-membered lactams that successively fused with cyclopropane and cyclopentane rings was established to be trans-5,8,9,10,10a,10b-hexahydro-5-methylcyclopenta[3,4]cyclopropa[1,2-d]benzazepine-6,7-dione by X-ray crystallographic analysis. The pathways leading to the formation of all of these products arising from beta-scissions are discussed.