<1R-(1α,3aβ,7aα)>-1-<(1R)-3-<(tert-butyldiphenylsilyl)oxy>-1-methylpropyl>octahydro-7a-methyl-4H-inden-4-one | 146434-11-9

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: <1R-(1α,3aβ,7aα)>-1-<(1R)-3-<(tert-butyldiphenylsilyl)oxy>-1-methylpropyl>octahydro-7a-methyl-4H-inden-4-one
• 英文别名: (1R-(1α,3aβ,7aα))-1-{(1R)-3-[(tert-butyldiphenylsilyl)oxy]-1-methylpropyl}octahydro-7a-methyl-4H-inden-4-one；(1R,3aR,7aR)-1-[(2R)-4-[tert-butyl(diphenyl)silyl]oxybutan-2-yl]-7a-methyl-2,3,3a,5,6,7-hexahydro-1H-inden-4-one
• CAS: 146434-11-9
• 化学式: C₃₀H₄₂O₂Si
• 分子量: 462.748
• InChiKey: ONUYOZFNBQLQOA-CFHNXLEQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.37
• 重原子数：
  33
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  <1R-(1α,3aβ,7aα)>-1-<(1R)-3-<(tert-butyldiphenylsilyl)oxy>-1-methylpropyl>octahydro-7a-methyl-4H-inden-4-one 在 palladium on activated charcoal lithium aluminium tetrahydride 、 重铬酸吡啶 、 四丁基氟化铵 、 氢气 、 potassium hydride 、 sodium hydride 、 magnesium 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 、 二氯甲烷 、 paraffin 为溶剂， 25.0 ℃ 、101.33 kPa 条件下， 反应 108.67h， 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：

  <1R-(1α,5α,7aα)>-1-<(1R)-3-<(tert-butyldiphenylsilyl)oxy>-1-methylpropyl>-2,3,5,6,7,7a-hexahydro-4-methoxy-5-<(methoxycarbonyl)oxy>-7a-methyl-1H-indene 在 RhCl(PPh₃)3 咪唑 、 sodium tetrahydroborate 、 重铬酸吡啶 、 cerium(III) chloride 、 氢气 作用下， 以 乙醇 、 二氯甲烷 、 二甲基亚砜 、 N,N-二甲基甲酰胺 为溶剂， -78.0~100.0 ℃ 、101.33 kPa 条件下， 反应 34.0h， 生成 <1R-(1α,3aβ,7aα)>-1-<(1R)-3-<(tert-butyldiphenylsilyl)oxy>-1-methylpropyl>octahydro-7a-methyl-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

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.