(1R,3S,5R)-6,6-dimethyl-3-(phenylseleno)bicyclo<3.1.1>heptan-2-one | 135503-45-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1R,3S,5R)-6,6-dimethyl-3-(phenylseleno)bicyclo<3.1.1>heptan-2-one
• 英文别名: 3-(phenylselenyl)nopinone
• CAS: 135503-45-6
• 化学式: C₁₅H₁₈OSe
• 分子量: 293.267
• InChiKey: PXLQCLSPYJUUIV-KGYLQXTDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.44
• 重原子数：
  17.0
• 可旋转键数：
  2.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (1R,3S,5R)-6,6-dimethyl-3-(phenylseleno)bicyclo<3.1.1>heptan-2-one 在 吡啶 、 Celite 、 双氧水 、 pyridinium chlorochromate 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 7.5h， 生成 马鞭草烯醇
  参考文献：
  名称：

  Efficient synthesis of (1S,5S)-4-alkyl-6,6-dimethylbicyclo[3.1.1]hept-3-en-2-ones from (1R,5S)-(+)-nopinone and preparation of some chiral building blocks suitable for the asymmetric synthesis

  摘要：

  A general and convenient transformation of (1R,5S)-(+)-nopinone (1) into (1S,5S)-4-alkyl-6,6-dimethylbicyclo[3.1.1]hept-3-en-2-ones, i.e., (-)-verbenone (6a) as the simplest compound and its C(4)-alkyl homologs 6b-f, via (+)-apoverbenone (7) is developed and applied, starting with 6a,e, to the syntheses of (4R,5R)-1-acetoxy-4-isopropenyl-5-methyl-5-vinyl-1-cyclohexene (12a) and (4R,5S)- and (4R,5R)-1-acetoxy-5-(3-butenyl)-4-isopropenyl-5-methyl-1-cyclohexene (12b and 12c), in connection with a search for chiral building blocks suitable for the asymmetric synthesis. Preparation of 12a indicates the formal synthesis of the elemanoid sesquiterpenes (-)-beta-elemenone and (-)-eleman-8beta,12-olide.

  DOI：

  10.1021/jo00067a026
• 作为产物：
  描述：

  (1R)-(+)-诺蒎酮 、 二苯基二硒醚 在 selenium(IV) oxide 、 甲烷磺酸 作用下， 以 二氯甲烷 为溶剂， 以87%的产率得到(1R,3S,5R)-6,6-dimethyl-3-(phenylseleno)bicyclo<3.1.1>heptan-2-one
  参考文献：
  名称：

  Efficient synthesis of (1S,5S)-4-alkyl-6,6-dimethylbicyclo[3.1.1]hept-3-en-2-ones from (1R,5S)-(+)-nopinone and preparation of some chiral building blocks suitable for the asymmetric synthesis

  摘要：

  A general and convenient transformation of (1R,5S)-(+)-nopinone (1) into (1S,5S)-4-alkyl-6,6-dimethylbicyclo[3.1.1]hept-3-en-2-ones, i.e., (-)-verbenone (6a) as the simplest compound and its C(4)-alkyl homologs 6b-f, via (+)-apoverbenone (7) is developed and applied, starting with 6a,e, to the syntheses of (4R,5R)-1-acetoxy-4-isopropenyl-5-methyl-5-vinyl-1-cyclohexene (12a) and (4R,5S)- and (4R,5R)-1-acetoxy-5-(3-butenyl)-4-isopropenyl-5-methyl-1-cyclohexene (12b and 12c), in connection with a search for chiral building blocks suitable for the asymmetric synthesis. Preparation of 12a indicates the formal synthesis of the elemanoid sesquiterpenes (-)-beta-elemenone and (-)-eleman-8beta,12-olide.

  DOI：

  10.1021/jo00067a026

文献信息

• Synthesis of racemic and optically active .DELTA.9-tetrahydrocannabinol (THC) metabolites
  作者：Craig Siegel、Patrick M. Gordon、David B. Uliss、G. Richard Handrick、Haldean C. Dalzell、Raj. K. Razdan

  DOI：10.1021/jo00024a031

  日期：1991.11

  The preparation of racemic and optically active DELTA-9-THC metabolites is described from synthon 13. Racemic synthon 13 is prepared in four steps (46%) from Danishefsky's diene. Optically active synthon 13 is prepared from perillaldehyde via the enone 22 in six steps (23% yield). Alternatively, nopinone can be converted to 13 in three steps (50% yield) via a cyclobutane ring cleavage. The acid-catalyzed condensation of 13 with olivetol (6a) and subsequent conversion to 11-hydroxy and 9-carboxyl DELTA-9-THC metabolites 2a and 4a is described, as well as the preparation of 1',1'-dimethylheptyl THC analogues 2b, 3b, and 4b from 5-(1',1'-dimethylheptyl)resorcinol (6c).