(+)-(1R,2R,3S,4S,6R,7R)-1,6-Dimethyl-4-endo-isopropyl-2-(1-naphthyl)tricyclo<4.3.1.0^3,7>decan-9-one

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (+)-(1R,2R,3S,4S,6R,7R)-1,6-Dimethyl-4-endo-isopropyl-2-(1-naphthyl)tricyclo<4.3.1.0^3,7>decan-9-one
• 英文别名: (1R,2R,3R,4S,6R,7R)-1,6-dimethyl-2-naphthalen-1-yl-4-propan-2-yltricyclo[4.3.1.03,7]decan-9-one
• 化学式: C₂₅H₃₀O
• 分子量: 346.513
• InChiKey: RZVVOXGIVGSMFP-RWVWRCSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  26
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  (R)-Carvone 在 palladium on activated charcoal N-溴代丁二酰亚胺(NBS) 、 正丁基锂 、 偶氮二异丁腈 、 potassium tert-butylate 、 氢气 、 三正丁基氢锡 、 silica gel 、 三溴化硼 、 对甲苯磺酸 、 pyridinium chlorochromate 、 叔丁醇 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 苯 为溶剂， 反应 90.5h， 生成 (+)-(1R,2R,3S,4S,6R,7R)-1,6-Dimethyl-4-endo-isopropyl-2-(1-naphthyl)tricyclo<4.3.1.0^3,7>decan-9-one
  参考文献：
  名称：

  Chiral synthons from carvone. 9. Radical annulation strategy to chiral pupukeanones: total synthesis of (+)-10-exo-(1-naphthyl)pupukean-9-one and (+)-10-exo-(1-naphthyl)-5-epipupukean-9-ones

  摘要：

  Intramolecular alkylation reaction of the bromoenone 12, obtained from S-carvone in three steps, furnished the bicyclo[2.2.2]octenone 13. Contrary to the anticipated radical annulation reaction, the bicyclic bromides 14 and 15, obtained from the enone 13, generated exclusively the cyclopropane product 18 via a 3-exo-trig radical cyclization on reaction with nBu3SnH and AIBN, even in the presence of a large excess of a radicophile. On the other hand, bromoenone 24, synthesized from R-carvone via S-naphthylcarvone 21, underwent radical annulation reaction in the presence of radicophiles to furnish the isotwistanes 25-28 in a regio- and stereospecific manner. Hydrogenation of the olefin 34, obtained from the diketone 27 via a regiospecific Wittig reaction, furnished the naphthyl-5-epipupukean-9-one 33, whereas stereoselective hydrogenation of the enone 36, prepared from the keto ester 25 via a Grignard reaction and dehydration sequence, generated the naphthylpupukeanone 32.

  DOI：

  10.1021/jo00061a026

文献信息

• Chiral synthons from carvone. 9. Radical annulation strategy to chiral pupukeanones: total synthesis of (+)-10-exo-(1-naphthyl)pupukean-9-one and (+)-10-exo-(1-naphthyl)-5-epipupukean-9-ones
  作者：A. Srikrishna、P. Hemamalini、G. Veera Raghava Sharma

  DOI：10.1021/jo00061a026

  日期：1993.4

  Intramolecular alkylation reaction of the bromoenone 12, obtained from S-carvone in three steps, furnished the bicyclo[2.2.2]octenone 13. Contrary to the anticipated radical annulation reaction, the bicyclic bromides 14 and 15, obtained from the enone 13, generated exclusively the cyclopropane product 18 via a 3-exo-trig radical cyclization on reaction with nBu3SnH and AIBN, even in the presence of a large excess of a radicophile. On the other hand, bromoenone 24, synthesized from R-carvone via S-naphthylcarvone 21, underwent radical annulation reaction in the presence of radicophiles to furnish the isotwistanes 25-28 in a regio- and stereospecific manner. Hydrogenation of the olefin 34, obtained from the diketone 27 via a regiospecific Wittig reaction, furnished the naphthyl-5-epipupukean-9-one 33, whereas stereoselective hydrogenation of the enone 36, prepared from the keto ester 25 via a Grignard reaction and dehydration sequence, generated the naphthylpupukeanone 32.