(2R,3R)-3-[(2R)-4-hydroxybutan-2-yl]-2-methylcyclopentan-1-one | 146433-98-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3R)-3-[(2R)-4-hydroxybutan-2-yl]-2-methylcyclopentan-1-one
• CAS: 146433-98-9
• 化学式: C₁₀H₁₈O₂
• 分子量: 170.252
• InChiKey: KQZSHDLIISLLGY-IWSPIJDZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 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：

  (2R,3R)-3-[(2R)-4-hydroxybutan-2-yl]-2-methylcyclopentan-1-one 在 palladium on activated charcoal 、 RhCl(PPh₃)3 吡啶 、 咪唑 、 叔丁基过氧化氢 、 4-二甲氨基吡啶 、 氢氧化钾 、 sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 重铬酸吡啶 、 cerium(III) chloride 、 草酰氯 、 bis(acetylacetonate)oxovanadium 、 四丁基氟化铵 、 氢气 、 potassium hydride 、 sodium hydride 、 magnesium 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 乙醇 、 二氯甲烷 、 水 、 二甲基亚砜 、 1,2-二氯乙烷 、 N,N-二甲基甲酰胺 、 paraffin 、 苯 为溶剂， -78.0~100.0 ℃ 、101.33 kPa 条件下， 反应 180.84h， 生成 (1R,3aR,7aR)-1-{(1R)-1,5-dimethyl-5-[(trimethylsilyl)oxy]hexyl}-7a-methyloctahydro-4H-inden-4-one
  参考文献：
  名称：

  Stereoselective synthesis of cyclopentanones by reductive cleavage of 6-oxonorbornane-2-carboxylates and its application to the synthesis of 1.alpha.,25-dihydroxyvitamin D3 CD ring

  摘要：

  A novel chiral synthesis of the CD-ring 2 of 1alpha,25-dihydroxyvitamin D3 (1a) is described. The optically active D-ring keto ester 3c was prepared by reductive cleavage of 6-oxonorbornane-2-carboxylate 4c with lithium naphthalenide. 1,2-Transposition of enone 15, which was obtained by Robinson annulation of 14, was accomplished via thermolysis of the allylic carbonate 29 at 100-degrees-C to give enone 16. Reduction of ketone 16 with NaBH4-CeCl3 followed by hydrogenation with RhCl-(PPh3)3 catalyst gave trans-indanol 32, which was transformed to intermediate 2.

  DOI：

  10.1021/jo00058a032
• 作为产物：
  描述：

  4-((tert-butyldimethylsilyl)oxy)-2-methylbutan-1-ol 在 palladium on activated charcoal 正丁基锂 、 草酰氯 、 三氟化硼乙醚 、 氢气 、 二甲基亚砜 、 三苯基膦 作用下， 以 乙醇 为溶剂， 25.0 ℃ 、101.33 kPa 条件下， 反应 12.0h， 生成 (2R,3R)-3-[(2R)-4-hydroxybutan-2-yl]-2-methylcyclopentan-1-one
  参考文献：
  名称：

  Stereoselective Preparation of Vitamin D Precursors Using the Intramolecular Coupling of Alkynes and Cyclopropylcarbene−Chromium Complexes:  A Formal Total Synthesis of (±)-Vitamin D₃

  摘要：

  The intramolecular coupling of alkynes and cyclopropylcarbene-chromium complexes has been examined. Complexes that feature a stereogenic center at the propargylic position of the alkyne-carbene tether are the focus of this paper. The reaction produces a cyclopentadienone intermediate fused to an oxygen heterocycle, which is reduced to the corresponding cyclopentenone under the reaction conditions (100 degrees C in aqueous toluene). The preexisting stereogenic center has a powerful influence on the reduction of the cyclopentadienone ring, and predominantly a single diastereomer is produced in the reaction. Reductive cleavage of the heterocyclic ring with retention of stereochemistry affords compounds featuring a stereocenter on the five-membered ring and on a side chain. Use of the above reaction processes for the synthesis of the vitamin D precursor de-ABC-cholestan-14-one is also discussed.

  DOI：

  10.1021/jo972186z

文献信息

• Stereoselective synthesis of cyclopentanones by reductive cleavage of 6-oxonorbornane-2-carboxylates and its application to the synthesis of 1.alpha.,25-dihydroxyvitamin D3 CD ring
  作者：Kazuo Nagasawa、Naoto Matsuda、Yasuo Noguchi、Masahiro Yamanashi、Yoshiro Zako、Isao Shimizu

  DOI：10.1021/jo00058a032

  日期：1993.3

  A novel chiral synthesis of the CD-ring 2 of 1alpha,25-dihydroxyvitamin D3 (1a) is described. The optically active D-ring keto ester 3c was prepared by reductive cleavage of 6-oxonorbornane-2-carboxylate 4c with lithium naphthalenide. 1,2-Transposition of enone 15, which was obtained by Robinson annulation of 14, was accomplished via thermolysis of the allylic carbonate 29 at 100-degrees-C to give enone 16. Reduction of ketone 16 with NaBH4-CeCl3 followed by hydrogenation with RhCl-(PPh3)3 catalyst gave trans-indanol 32, which was transformed to intermediate 2.
• Stereoselective Preparation of Vitamin D Precursors Using the Intramolecular Coupling of Alkynes and Cyclopropylcarbene−Chromium Complexes:  A Formal Total Synthesis of (±)-Vitamin D₃
  作者：Jingbo Yan、James W. Herndon

  DOI：10.1021/jo972186z

  日期：1998.4.1

  The intramolecular coupling of alkynes and cyclopropylcarbene-chromium complexes has been examined. Complexes that feature a stereogenic center at the propargylic position of the alkyne-carbene tether are the focus of this paper. The reaction produces a cyclopentadienone intermediate fused to an oxygen heterocycle, which is reduced to the corresponding cyclopentenone under the reaction conditions (100 degrees C in aqueous toluene). The preexisting stereogenic center has a powerful influence on the reduction of the cyclopentadienone ring, and predominantly a single diastereomer is produced in the reaction. Reductive cleavage of the heterocyclic ring with retention of stereochemistry affords compounds featuring a stereocenter on the five-membered ring and on a side chain. Use of the above reaction processes for the synthesis of the vitamin D precursor de-ABC-cholestan-14-one is also discussed.