1β,6β,7β-7-hydroxymethyl-1,5,5,6-tetramethylbicyclo<4.3.0>-nonan-8-one | 145373-04-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1β,6β,7β-7-hydroxymethyl-1,5,5,6-tetramethylbicyclo<4.3.0>-nonan-8-one
• 英文别名: (1R,3aR,7aR)-1-(hydroxymethyl)-3a,7,7,7a-tetramethyl-3,4,5,6-tetrahydro-1H-inden-2-one
• CAS: 145373-04-2
• 化学式: C₁₄H₂₄O₂
• 分子量: 224.343
• InChiKey: ARIYOTIQYLFICG-LERXQTSPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  叔丁基二甲基氯硅烷 、 1β,6β,7β-7-hydroxymethyl-1,5,5,6-tetramethylbicyclo<4.3.0>-nonan-8-one 在 4-二甲氨基吡啶 吡啶 作用下， 反应 36.0h， 以91%的产率得到(1β,6β,7β)-7-<<(tert-Butyldimethylsilyl)oxy>methyl>-1,5,5,6-tetramethylbicyclo<4.3.0>nonan-8-one
  参考文献：
  名称：

  Stereospecific construction of multiple contiguous quaternary carbons. Total synthesis of (±)-cis,anti,cis-1,8,12,12-tetramethyl-4-oxatricyclo[6.4.0.02,6]dodecan-3-ol, a thapsane isolated from Thapsia villosa var minor

  摘要：

  The details of the first total synthesis of a natural thapsane 1g containing three contiguous quaternary carbon atoms, starting from cyclogeraniol (9) is described. The Claisen rearrangement of 9 with methoxypropene in the presence of acatalytic amount of propionic acid produced ketone 10. Rhodium acetate-catalyzed intramolecular cyclopropanation of alpha-diazo-beta-keto ester 12, obtained from 10 via beta-keto ester 8, furnished cyclopropyl keto ester 7. Lithium in liquid ammonia reductive cleavage of cyclopropyl compound 7 gave a 1:1 mixture of hydrindanone 6 and ketol 13. Wittig methylenation of 6 furnished ester 21. Epoxidation of 21, followed by BF3-OEt2-catalyzed rearrangement of epoxide 23 afforded hemiacetal 25. Treatment of hemiacetal 25 with triethylsilane in trifluoroacetic acid furnished lactone 22, a degradation product of various thapsanes. Finally, DIBAH reduction of lactone 22 generated the thapsane 1g.

  DOI：

  10.1021/jo00079a020
• 作为产物：
  描述：

  3α,6β-3-hydroxymethyl-6,10,10-trimethyltricyclo<4.4.0.0^1,3>decan-4-one 在 氨 、 lithium 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 以63%的产率得到1β,6β,7β-7-hydroxymethyl-1,5,5,6-tetramethylbicyclo<4.3.0>-nonan-8-one
  参考文献：
  名称：

  三环[4.4.0.0 1,3 ]癸烷在丙烷丙烷环上裂解为氢丙烷和十氢化萘系统的区域控制

  摘要：

  环丙基β-酮酸酯的锂-液氨还原反应提供了1：1的氢化丙烷和十氢化萘体系混合物，以及。而在相同条件下酮和苯并氢呋喃酮和; 和羟基酯提供的萘烷系统，通过无论是C的区域专一性裂解3 C 2键或C 3 C 1个键。

  DOI：

  10.1016/s0040-4020(01)81189-3

文献信息

• Stereospecific construction of multiple contiguous quaternary carbons. Total synthesis of (±)-cis,anti,cis-1,8,12,12-tetramethyl-4-oxatricyclo[6.4.0.02,6]dodecan-3-ol, a thapsane isolated from Thapsia villosa var minor
  作者：A. Srikrishna、K. Krishnan

  DOI：10.1021/jo00079a020

  日期：1993.12

  The details of the first total synthesis of a natural thapsane 1g containing three contiguous quaternary carbon atoms, starting from cyclogeraniol (9) is described. The Claisen rearrangement of 9 with methoxypropene in the presence of acatalytic amount of propionic acid produced ketone 10. Rhodium acetate-catalyzed intramolecular cyclopropanation of alpha-diazo-beta-keto ester 12, obtained from 10 via beta-keto ester 8, furnished cyclopropyl keto ester 7. Lithium in liquid ammonia reductive cleavage of cyclopropyl compound 7 gave a 1:1 mixture of hydrindanone 6 and ketol 13. Wittig methylenation of 6 furnished ester 21. Epoxidation of 21, followed by BF3-OEt2-catalyzed rearrangement of epoxide 23 afforded hemiacetal 25. Treatment of hemiacetal 25 with triethylsilane in trifluoroacetic acid furnished lactone 22, a degradation product of various thapsanes. Finally, DIBAH reduction of lactone 22 generated the thapsane 1g.
• Regiocontrol in the cyclopropane ring cleavage of tricyclo[4.4.0.01,3]decanes to hydrindane and decalin systems
  作者：Adusumilli Srikrishna、Kathiresan Krishnan、Channabasaveshwar V. Yelamaggad

  DOI：10.1016/s0040-4020(01)81189-3

  日期：1992.1

  Lithium-liquid ammonia reduction of the cyclopropyl β-ketoester furnished a 1:1 mixture of hydrindane and decalin systems and . Whereas under the same conditions the ketones and furnished the hydrindanones and ; and the hydroxy ester furnished the decalin system , via the regiospecific cleavage of either C3C2 bond or C3C1 bond.

  环丙基β-酮酸酯的锂-液氨还原反应提供了1：1的氢化丙烷和十氢化萘体系混合物，以及。而在相同条件下酮和苯并氢呋喃酮和; 和羟基酯提供的萘烷系统，通过无论是C的区域专一性裂解3 C 2键或C 3 C 1个键。