(R)-(E)-2-[6,10-dimethyl-10-(triethylsilanyloxy)undec-1-enyl]-5,5-dimethyl[1,3,2]dioxaborolane | 387834-47-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 硼酸衍生物
• 英文名称: (R)-(E)-2-[6,10-dimethyl-10-(triethylsilanyloxy)undec-1-enyl]-5,5-dimethyl[1,3,2]dioxaborolane
• 英文别名: [(E,6R)-11-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-2,6-dimethylundec-10-en-2-yl]oxy-triethylsilane
• CAS: 387834-47-1
• 化学式: C₂₄H₄₉BO₃Si
• 分子量: 424.548
• InChiKey: NJDYITLEKUFMIX-PGPKDTDWSA-N

物化性质

• 沸点：
  440.6±47.0 °C(Predicted)
• 密度：
  0.89±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.42
• 重原子数：
  29
• 可旋转键数：
  14
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 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：

  (R)-(E)-2-[6,10-dimethyl-10-(triethylsilanyloxy)undec-1-enyl]-5,5-dimethyl[1,3,2]dioxaborolane 在 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 、 氢氧化钾 、 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 生成 (1S,3S)-5-[(E)-(R)-11-Hydroxy-7,11-dimethyl-dodec-2-en-(Z)-ylidene]-4-methylene-cyclohexane-1,3-diol
  参考文献：
  名称：

  New Convergent Synthesis of 1α,25-Dihydroxyvitamin D₃ and Its Analogues by Suzuki−Miyaura Coupling between A-Ring and C,D-Ring Parts

  摘要：

  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.

  DOI：

  10.1021/jo0353435
• 作为产物：
  描述：

  (S)-(+)-溴化香茅酯 在 咪唑 、 Pinene 、 dimethyl sulfide borane 、 magnesium 、 乙醛 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 23.5h， 生成 (R)-(E)-2-[6,10-dimethyl-10-(triethylsilanyloxy)undec-1-enyl]-5,5-dimethyl[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。
• 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.
• 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.