(E)-4-(tert-butyldimethylsilanyloxy)oct-2-en-1-ol | 1040285-12-8

• 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: (E)-4-(tert-butyldimethylsilanyloxy)oct-2-en-1-ol
• 英文别名: (E)-4-[tert-butyl(dimethyl)silyl]oxyoct-2-en-1-ol
• CAS: 1040285-12-8
• 化学式: C₁₄H₃₀O₂Si
• 分子量: 258.476
• InChiKey: QQRBYYWTMJNDAF-PKNBQFBNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.12
• 重原子数：
  17
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-4-(tert-butyldimethylsilanyloxy)oct-2-en-1-ol 、 三氯乙腈 在 sodium hydride 作用下， 以 乙醚 为溶剂， 以99%的产率得到2,2,2-trichloroacetimidic acid (E)-4-(tert-butyldimethylsilanyloxy)oct-2-enyl ester
  参考文献：
  名称：

  Ether-directed diastereoselectivity in catalysed Overman rearrangement: comparative studies of metal catalysts

  摘要：

  Ether-directed diastereoselectivity in Overman rearrangement of delta-methoxy and delta-TBDMSO substituted allylic trichloroacetimidates has been explored using PtCl2, PtCl4, AuCl and AuCl3 catalysts in comparison with commonly used Pd(II) catalysts. For both substrates the use of PtCl2 catalyst gave notably improved anti/syn-ratio of 1,2-aminoalcohol derivatives (anti/syn=11:1 for 5-methoxy; 6:1 for delta-TBDMSO) compared to all metal catalysts known to promote Overman rearrangement. Formation of 2-trichloromethyloxazoline was observed as a dominant side reaction in the metal catalysed rearrangement of a-methoxy substituted allylic trichloroacetimidates considerably reducing the yield of the desired product. This side reaction was suppressed when delta-TBDMS-ether was used as a directing group. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2008.03.099
• 作为产物：
  描述：

  (E)-4-(tert-butyldimethylsilanyloxy)oct-2-enoic acid methyl ester 在 二异丁基氢化铝 作用下， 以 乙醚 、 正己烷 为溶剂， 以92%的产率得到(E)-4-(tert-butyldimethylsilanyloxy)oct-2-en-1-ol
  参考文献：
  名称：

  Ether-directed diastereoselectivity in catalysed Overman rearrangement: comparative studies of metal catalysts

  摘要：

  Ether-directed diastereoselectivity in Overman rearrangement of delta-methoxy and delta-TBDMSO substituted allylic trichloroacetimidates has been explored using PtCl2, PtCl4, AuCl and AuCl3 catalysts in comparison with commonly used Pd(II) catalysts. For both substrates the use of PtCl2 catalyst gave notably improved anti/syn-ratio of 1,2-aminoalcohol derivatives (anti/syn=11:1 for 5-methoxy; 6:1 for delta-TBDMSO) compared to all metal catalysts known to promote Overman rearrangement. Formation of 2-trichloromethyloxazoline was observed as a dominant side reaction in the metal catalysed rearrangement of a-methoxy substituted allylic trichloroacetimidates considerably reducing the yield of the desired product. This side reaction was suppressed when delta-TBDMS-ether was used as a directing group. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2008.03.099

文献信息

• Ether-directed diastereoselectivity in catalysed Overman rearrangement: comparative studies of metal catalysts
  作者：Ieva Jaunzeme、Aigars Jirgensons

  DOI：10.1016/j.tet.2008.03.099

  日期：2008.6

  Ether-directed diastereoselectivity in Overman rearrangement of delta-methoxy and delta-TBDMSO substituted allylic trichloroacetimidates has been explored using PtCl2, PtCl4, AuCl and AuCl3 catalysts in comparison with commonly used Pd(II) catalysts. For both substrates the use of PtCl2 catalyst gave notably improved anti/syn-ratio of 1,2-aminoalcohol derivatives (anti/syn=11:1 for 5-methoxy; 6:1 for delta-TBDMSO) compared to all metal catalysts known to promote Overman rearrangement. Formation of 2-trichloromethyloxazoline was observed as a dominant side reaction in the metal catalysed rearrangement of a-methoxy substituted allylic trichloroacetimidates considerably reducing the yield of the desired product. This side reaction was suppressed when delta-TBDMS-ether was used as a directing group. (C) 2008 Elsevier Ltd. All rights reserved.