(3R)-3-[(1R,3aR,4S,7aR)-7a-methyl-4-phenylmethoxy-1,2,3,3a,4,5,6,7-octahydroinden-1-yl]butanal | 96845-35-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (3R)-3-[(1R,3aR,4S,7aR)-7a-methyl-4-phenylmethoxy-1,2,3,3a,4,5,6,7-octahydroinden-1-yl]butanal
• CAS: 96845-35-1
• 化学式: C₂₁H₃₀O₂
• 分子量: 314.468
• InChiKey: NBJPCVFNTDYOIG-BVJIBDCISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  (3R)-3-[(1R,3aR,4S,7aR)-7a-methyl-4-phenylmethoxy-1,2,3,3a,4,5,6,7-octahydroinden-1-yl]butanal 在 palladium on activated charcoal 重铬酸吡啶 、 氢气 、 sodium hydride 、 magnesium 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 paraffin 为溶剂， 25.0 ℃ 、101.33 kPa 条件下， 反应 97.0h， 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：

  (R)-3-((1R,3aR,4S,7aR)-4-Benzyloxy-7a-methyl-octahydro-inden-1-yl)-butyronitrile 在 二异丁基氢化铝 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 0.5h， 生成 (3R)-3-[(1R,3aR,4S,7aR)-7a-methyl-4-phenylmethoxy-1,2,3,3a,4,5,6,7-octahydroinden-1-yl]butanal
  参考文献：
  名称：

  A highly stereoselective route to calcitriol lactone

  摘要：

  DOI：

  10.1021/jo00214a046

文献信息

• Asymmetric Catalysis of Nozaki−Hiyama Allylation and Methallylation with A New Tridentate Bis(oxazolinyl)carbazole Ligand
  作者：Masahiro Inoue、Takahiro Suzuki、Masahisa Nakada

  DOI：10.1021/ja021243p

  日期：2003.2.1

  the asymmetric catalysis of Nozaki-Hiyama allylation and methallylation. Various aldehydes were allylated or methallylated with good enantioselectivity (86-96%), and a key intermediate of calcitriol lactone synthesis was also obtained with excellent diastereoselectivity (97% de, 91%). The enantioselective reaction catalyzed by this Cr-ligand complex is applicable to a broad range of aldehydes and has

  这项工作描述了对 Nozaki-Hiyama 烯丙基化和甲基烯丙基化的不对称催化有效的新三齿配体的开发。各种醛以良好的对映选择性（86-96%）烯丙基化或甲基烯丙基化，并以优异的非对映选择性（97% de, 91%）获得骨化三醇内酯合成的关键中间体。由这种 Cr-配体配合物催化的对映选择性反应适用于广泛的醛类，在天然产物合成方面具有巨大潜力。这种配体的另一个显着特征是 Cr-配体复合物的稳定性，它在对映选择性反应后回收并循环两次，而不会降低对映选择性和产率。
• A convergent route to calcitriol lactone via reductive cleavage of an enantiopure glycidyl ether
  作者：Raymond E. Conrow

  DOI：10.1016/s0040-4039(00)73879-2

  日期：1993.8

  ether of (S)-2-methylglycidol with lithium 4,4′-di-t-butylbiphenylide, addition of aldehyde 3 to the resulting β-lithioalkoxide, followed by acidic hydrolysis, yields the advanced (23S,25R)-calcitriol lactone intermediate 4 plus its 23R epimer (∼1:1, 69%).

  （S）-2-甲基缩水甘油的（（1-甲基-1-甲氧基）乙基）醚与4,4'-二叔丁基联苯锂的还原裂解，向所得β-硫代醇盐中添加醛3，然后通过酸性水解，得到高级的（23S，25R）-骨化三醇内酯中间体4加上其23R差向异构体（〜1∶1，69 ％）。
• Non-chelation controlled 1,3-asymmetric induction in β-chiral acylsilanes
  作者：Masahisa Nakada、Yasuharu Urano、Susumu Kobayashi、Masaji Ohno

  DOI：10.1016/s0040-4039(00)75805-9

  日期：1994.1

  The diastereoselectivity of nucleophilic adition to beta-chiral acylsilanes is examined, and our method is applied to the stereoselective synthesis of calcitriol lactone, a major metabolite of vitamine D-3.
• 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.
• A highly stereoselective route to calcitriol lactone
  作者：William S. Johnson、Ming Fai Chan

  DOI：10.1021/jo00214a046

  日期：1985.7