4-(tributylstannyl)pent-4-en-1-ol | 130826-44-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-(tributylstannyl)pent-4-en-1-ol
• 英文别名: 5-hydroxy-2-tri-n-butylstannyl-1-pentene
• CAS: 130826-44-7
• 化学式: C₁₇H₃₆OSn
• 分子量: 375.182
• InChiKey: BFJNIYQQLQMMED-UHFFFAOYSA-N

物化性质

• 沸点：
  394.7±44.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  19
• 可旋转键数：
  13
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,6,6-trimethylcyclohex-1-en-1-yl trifluoromethanesulfonate 、 4-(tributylstannyl)pent-4-en-1-ol 在 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 三苯胂 作用下， 以 N-甲基吡咯烷酮 为溶剂， 反应 16.0h， 以25%的产率得到4-(2,6,6-Trimethylcyclohexen-1-yl)pent-4-en-1-ol
  参考文献：
  名称：

  Stereocontrolled Synthesis of 6-s-cis- and 6-s-trans-Locked 9Z-Retinoids by Hydroxyl-Accelerated Stille Coupling of (Z)-Tri-n-Butylstannylbut-2-en-1-ol and Bicyclic Dienyl Triflates

  摘要：

  Analogues of 9-cis-retinoic acid with locked 6-s-cis and 6-s-trans conformations have been stereoselectively synthesized using a Stille coupling reaction between bicyclic dienyl triflates (5 and 6, respectively) and (Z)-tributylstannylbut-2-en-1-ol (7) to stablish the Z geometry of the polyenic side chain. The mild conditions (25 degrees C, 30 min) of this coupling stand in contrast to the reluctance of the isomeric (E)-tributylstannylbut-2-en-1-ol (18) to react with triflates 5/6. The significant rate differences experimentally observed in Stille reactions between isomeric (Z)- and (E)-tri-n-butylstannylalkenols in favor of the former isomer, even with highly hindered alkenyl triflates, is ascribed to internal coordination of palladium to the heteroatom in the presumably rate-limiting transmetalation step. Dienals and trienals with an E geometry, which are not efficiently available by direct coupling of the corresponding triflates and E-stannanes, can in turn be obtained by isomerization of their Z-isomers.

  DOI：

  10.1021/jo9917588
• 作为产物：
  描述：

  4-戊炔-1-醇 、 三正丁基氢锡 在 Cp*Fe(1,2-Ph₂PC₆H₄NH) 作用下， 以 甲苯 为溶剂， 反应 0.28h， 以81%的产率得到4-(tributylstannyl)pent-4-en-1-ol
  参考文献：
  名称：

  炔烃的铁催化区域发散氢化锡化：Fe(IV)-H 与 Fe(II)-亚乙烯基的中间体

  摘要：

  我们报告了一种铁系统 Cp*Fe(1,2-R2PC6H4X)，它通过调节离子金属-杂原子键 (Fe-X) 的反应性来控制炔烃的马尔科夫尼科夫和反马尔科夫尼科夫氢氢化。将 nBu3SnH 依次添加到铁-酰胺基催化剂 (1, X = HN-, R = Ph) 中提供了二锡基 Fe(IV)-H 物种，负责跨 C≡C 键的 Sn-H 键的顺式加成生产支链α-乙烯基锡烷。通过芳基氧化铁催化剂 (2, X = O-, R = Cy) 活化炔烃的 C(sp)-H 键，得到亚乙烯基铁 (II) 中间体，允许 Sn-H 与产生β-乙烯基锡烷的末端碳。这些催化反应表现出优异的区域选择性和广泛的官能团兼容性，能够大规模合成多种乙烯基锡烷。

  DOI：

  10.1021/jacs.0c11448

文献信息

• Barbero, Asuncion; Cuadrado, Purificacion; Fleming, Ian, Journal of the Chemical Society. Perkin transactions I, 1992, # 3, p. 327 - 332
  作者：Barbero, Asuncion、Cuadrado, Purificacion、Fleming, Ian、Gonzalez, Ana M.、Pulido, Francisco J.

  DOI：——

  日期：——
• Singh, Shankar; Oehlshlager, Allan C., Canadian Journal of Chemistry, 1991, vol. 69, # 12, p. 1872 - 1880
  作者：Singh, Shankar、Oehlshlager, Allan C.

  DOI：——

  日期：——
• Iron-Catalyzed Regiodivergent Hydrostannation of Alkynes: Intermediacy of Fe(IV)–H versus Fe(II)–Vinylidene
  作者：Jianguo Liu、Heng Song、Tianlin Wang、Jiong Jia、Qing-Xiao Tong、Chen-Ho Tung、Wenguang Wang

  DOI：10.1021/jacs.0c11448

  日期：2021.1.13

  iron-aryloxide catalyst (2, X = O-, R = Cy) affords an iron(II) vinylidene intermediate, allowing for gem-addition of the Sn-H to the terminal-carbon producing β-vinylstannanes. These catalytic reactions exhibit excellent regioselectivity and broad functional group compatibility and enable the large-scale synthesis of diverse vinylstannanes. Many new reactions have been established based on such a synthetic

  我们报告了一种铁系统 Cp*Fe(1,2-R2PC6H4X)，它通过调节离子金属-杂原子键 (Fe-X) 的反应性来控制炔烃的马尔科夫尼科夫和反马尔科夫尼科夫氢氢化。将 nBu3SnH 依次添加到铁-酰胺基催化剂 (1, X = HN-, R = Ph) 中提供了二锡基 Fe(IV)-H 物种，负责跨 C≡C 键的 Sn-H 键的顺式加成生产支链α-乙烯基锡烷。通过芳基氧化铁催化剂 (2, X = O-, R = Cy) 活化炔烃的 C(sp)-H 键，得到亚乙烯基铁 (II) 中间体，允许 Sn-H 与产生β-乙烯基锡烷的末端碳。这些催化反应表现出优异的区域选择性和广泛的官能团兼容性，能够大规模合成多种乙烯基锡烷。
• Stereocontrolled Synthesis of 6-<i>s</i>-<i>cis</i>- and 6-<i>s</i>-<i>trans</i>-Locked 9<i>Z</i>-Retinoids by Hydroxyl-Accelerated Stille Coupling of (<i>Z</i>)-Tri-<i>n</i>-Butylstannylbut-2-en-1-ol and Bicyclic Dienyl Triflates
  作者：Beatriz Domínguez、Yolanda Pazos、Angel R. de Lera

  DOI：10.1021/jo9917588

  日期：2000.9.1

  Analogues of 9-cis-retinoic acid with locked 6-s-cis and 6-s-trans conformations have been stereoselectively synthesized using a Stille coupling reaction between bicyclic dienyl triflates (5 and 6, respectively) and (Z)-tributylstannylbut-2-en-1-ol (7) to stablish the Z geometry of the polyenic side chain. The mild conditions (25 degrees C, 30 min) of this coupling stand in contrast to the reluctance of the isomeric (E)-tributylstannylbut-2-en-1-ol (18) to react with triflates 5/6. The significant rate differences experimentally observed in Stille reactions between isomeric (Z)- and (E)-tri-n-butylstannylalkenols in favor of the former isomer, even with highly hindered alkenyl triflates, is ascribed to internal coordination of palladium to the heteroatom in the presumably rate-limiting transmetalation step. Dienals and trienals with an E geometry, which are not efficiently available by direct coupling of the corresponding triflates and E-stannanes, can in turn be obtained by isomerization of their Z-isomers.