(1R,3aS,7aR)-(E)-2-{1-[(R)-1,5-dimethyl-5-(trimethylsilanyloxy)hexyl]-7a-methyloctahydroinden-4-ylidenemethyl}-4,4,5,5-tetramethyl[1,3,2]dioxaborolane | 387834-49-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1R,3aS,7aR)-(E)-2-{1-[(R)-1,5-dimethyl-5-(trimethylsilanyloxy)hexyl]-7a-methyloctahydroinden-4-ylidenemethyl}-4,4,5,5-tetramethyl[1,3,2]dioxaborolane
• 英文别名: [(6R)-6-[(1R,3aS,4E,7aR)-7a-methyl-4-[(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methylidene]-2,3,3a,5,6,7-hexahydro-1H-inden-1-yl]-2-methylheptan-2-yl]oxy-trimethylsilane
• CAS: 387834-49-3
• 化学式: C₂₈H₅₃BO₃Si
• 分子量: 476.624
• InChiKey: YXYOJXIXQIAUJA-YSQGJKNPSA-N

物化性质

• 沸点：
  469.9±37.0 °C(Predicted)
• 密度：
  0.94±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.2
• 重原子数：
  33
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1R,3aS,7aR)-(E)-2-{1-[(R)-1,5-dimethyl-5-(trimethylsilanyloxy)hexyl]-7a-methyloctahydroinden-4-ylidenemethyl}-4,4,5,5-tetramethyl[1,3,2]dioxaborolane 在 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 、 氢氧化钾 、 氢氟酸 作用下， 以 四氢呋喃 、 水 为溶剂， 生成 (1S,3S)-5-[(2E)-2-[(1R,3aS,7aR)-1-[(2R)-6-羟基-6-甲基庚烷-2-基]-7a-甲基-2,3,3a,5,6,7-六氢-1H-茚-4-亚基]亚乙基]环己烷-1,3-二醇
  参考文献：
  名称：

  Novel Synthetic Approach to 19-nor-1α,25-Dihydroxyvitamin D₃ and Its Derivatives by Suzuki−Miyaura Coupling in Solution and on Solid Support

  摘要：

  [GRAPHICS]19-nor-1 alpha ,25-Dihydroxyvitamin D-3 was synthesized by the Suzuki-Miyaura coupling of the A-ring intermediate 3, which was efficiently prepared from readily available 5-(tert butyldimethylsilyl)oxycyclohex-2-enone (5), with the boronate compound of the C,D-ring portion. The method could be applied to a solid-phase synthesis to prepare the des-C,D derivatives of 19-nor-1 alpha ,25-dihydroxyvitamin D-3.

  DOI：

  10.1021/ol016908r
• 作为产物：
  描述：

  频哪醇 、 [(R)-6-{(E,3R,3aR)-7-(bromomethylene)octahydro-3a-methyl-1H-inden-3-yl}-2-methylheptan-2-yloxy]trimethylsilane 在 硼酸三异丙酯 、 叔丁基锂 、 magnesium sulfate 、 氯化铵 作用下， 以 乙醚 、 正戊烷 为溶剂， 反应 17.0h， 以79%的产率得到(1R,3aS,7aR)-(E)-2-{1-[(R)-1,5-dimethyl-5-(trimethylsilanyloxy)hexyl]-7a-methyloctahydroinden-4-ylidenemethyl}-4,4,5,5-tetramethyl[1,3,2]dioxaborolane
  参考文献：
  名称：

  Novel Synthetic Approach to 19-nor-1α,25-Dihydroxyvitamin D₃ and Its Derivatives by Suzuki−Miyaura Coupling in Solution and on Solid Support

  摘要：

  [GRAPHICS]19-nor-1 alpha ,25-Dihydroxyvitamin D-3 was synthesized by the Suzuki-Miyaura coupling of the A-ring intermediate 3, which was efficiently prepared from readily available 5-(tert butyldimethylsilyl)oxycyclohex-2-enone (5), with the boronate compound of the C,D-ring portion. The method could be applied to a solid-phase synthesis to prepare the des-C,D derivatives of 19-nor-1 alpha ,25-dihydroxyvitamin D-3.

  DOI：

  10.1021/ol016908r

文献信息

• Efficient Convergent Synthesis of 1α,25-Dihydroxyvitamin D₃ and Its Analogues by Suzuki−Miyaura Coupling
  作者：Takeshi Hanazawa、Akiko Koyama、Takeshi Wada、Eiko Morishige、Sentaro Okamoto、Fumie Sato

  DOI：10.1021/ol0274007

  日期：2003.2.1

  [reaction: see text] 1alpha,25-Dihydroxyvitamin D(3) was synthesized by the Suzuki-Miyaura coupling of the A-ring intermediate 1, which was efficiently prepared from readily available 1,7-enyne 2, with the corresponding boronate compound of the C,D-ring portion. The method was applied to prepare des-C,D analogues of 1alpha,25-dihydroxyvitamin D(3).

  [反应：请参见文本]通过A环中间体1的Suzuki-Miyaura偶联合成了1alpha，25-二羟基维生素D（3），该中间体是从容易获得的1,7-烯2与相应的硼酸酯化合物有效制备的C，D环部分。该方法适用于制备1α，25-二羟基维生素D（3）的des-C，D类似物。
• New Convergent Synthesis of 1α,25-Dihydroxyvitamin D₃ and Its Analogues by Suzuki−Miyaura Coupling between A-Ring and C,D-Ring Parts
  作者：Takeshi Hanazawa、Akiko Koyama、Kunio Nakata、Sentaro Okamoto、Fumie Sato

  DOI：10.1021/jo0353435

  日期：2003.12.1

  A new convergent method for the synthesis of 1alpha,25-dihydroxyvitamin D-3 and its analogues has been developed that involves efficient preparation of the A-ring part la, (Z)-(3S,5R)-1-bromomethylene-3,5-bis(tert-butyldimethylsilyloxy)-2-methylenecyclohexane, starting from epichlorohydrin (4) and its Suzuki-Miyaura coupling reaction with the C,D-ring part 12. Thus, (R)-4 was converted to (3S,5R)-5-(tert-butyldimethylsilyloxy)-8-(trimethylsilyl)-oct-1-en-7-yn-3-ol (3a) through a ten-step reaction sequence in 49% overall yield. Compound 3a thus obtained was treated with a Ti(O-i-Pr)(4)/2 i-PrMgCl reagent and then with NBS to afford (Z)-(1S,2S,5R)-2-bromomethyl-3-[bromo(trimethylsilyl)methylene]-5-(tert-butyldimethylsilyloxy)cyclohexanol (10a) in 51% yield, from which la was obtained in 87% yield by sequential treatment with TBSCl/imidazole, DBU, and Cs2CO3. The resulting A-ring intermediate la was reacted with alkenylboronate 12 in the presence of a PdCl2(dppf) catalyst to furnish 1alpha,25-dihydroxyvitamin D-3 in 82% yield after protodesilylation. Similarly, all of the other three possible stereoisomers of A-ring parts 1b, 1c, and 1d were prepared, from which 1-epi-, 3-epi-, and 1,3-di-epi-1alpha,25-dihydroxyvitamin D-3 were synthesized by coupling with 12 in excellent yield, respectively. Starting from la and 1c, des-C,D-I(x,25-dihydroxyvitamin D-3 analogues, retiferol 13 and its 3-epi derivative, were also prepared, respectively.
• Novel Synthetic Approach to 19-<i>nor</i>-1α,25-Dihydroxyvitamin D₃ and Its Derivatives by Suzuki−Miyaura Coupling in Solution and on Solid Support
  作者：Takeshi Hanazawa、Takeshi Wada、Tomoko Masuda、Sentaro Okamoto、Fumie Sato

  DOI：10.1021/ol016908r

  日期：2001.11.1

  [GRAPHICS]19-nor-1 alpha ,25-Dihydroxyvitamin D-3 was synthesized by the Suzuki-Miyaura coupling of the A-ring intermediate 3, which was efficiently prepared from readily available 5-(tert butyldimethylsilyl)oxycyclohex-2-enone (5), with the boronate compound of the C,D-ring portion. The method could be applied to a solid-phase synthesis to prepare the des-C,D derivatives of 19-nor-1 alpha ,25-dihydroxyvitamin D-3.