(-)-3-but-2-ynyloxy-pent-1-ene | 874770-96-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (-)-3-but-2-ynyloxy-pent-1-ene
• 英文别名: (3S)-3-but-2-ynoxypent-1-ene
• CAS: 874770-96-4
• 化学式: C₉H₁₄O
• 分子量: 138.21
• InChiKey: YURIYBXDPOVYOF-SECBINFHSA-N

物化性质

• 沸点：
  184.7±15.0 °C(Predicted)
• 密度：
  0.851±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (-)-3-but-2-ynyloxy-pent-1-ene 、 异丁醛 在 bis(1,5-cyclooctadiene)nickel (0) 三乙基硼 作用下， 反应 15.0h， 以24%的产率得到4-(1-ethyl-allyloxymethyl)-2-methyl-hex-4-en-3-ol
  参考文献：
  名称：

  Mechanistic Implications of Nickel-Catalyzed Reductive Coupling of Aldehydes and Chiral 1,6-Enynes

  摘要：

  [GRAPHICS]A study of nickel-catalyzed reductive coupling reactions of aldehydes and chiral 1,6-enynes has provided evidence for three distinct mechanistic pathways that govern regioselectivity in this transformation. In the absence of a phosphine additive, high regioselectivity and high diastereoselectivity are obtained as a direct result of coordination of both the alkyne and the olefin to the metal center during the C-C bond-forming step.

  DOI：

  10.1021/ol052719n
• 作为产物：
  描述：

  1-戊烯-3-醇 在 titanium(IV) isopropylate 、 sodium hydride 、 D-(-)-酒石酸二异丙酯 作用下， 以 四氢呋喃 、 二氯甲烷 、 正戊烷 为溶剂， 反应 10.5h， 生成 (-)-3-but-2-ynyloxy-pent-1-ene
  参考文献：
  名称：

  Directing effects of tethered alkenes in nickel-catalyzed coupling reactions of 1,6-enynes and aldehydes

  摘要：

  Nickel-catalyzed reductive coupling reactions of aldehydes and 1,6-enynes proceed in excellent regioselectivity in the absence of a phosphine, and the use of a monodentate phosphine additive leads to the formation of the opposite regioisomer with equally high selectivity. Both products are the result of the same fundamental mechanism, with the inversion of regioselectivity being the result of stereospecific ligand substitution at the metal center. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.03.122

文献信息

• Total Synthesis of (+)-Acutiphycin
  作者：Ryan M. Moslin、Timothy F. Jamison

  DOI：10.1021/jo701821h

  日期：2007.12.1

  [GRAPHICS]Synthetic studies toward the total synthesis of (+)-acutiphycin (1) resulted in the discovery of additive-free, highly regioselective nickel -catalyzed reductive coupling reactions of aldehydes and 1,6-enynes and the construction of an advanced intermediate in studies directed toward the synthesis of 1. Ultimately, although not employing the nickel-catalyzed reaction, a highly convergent total synthesis of (+)-acutiphycin featuring an intermolecular SMI2-mediated Reformatsky coupling reaction and macrolactonization initiated by a retro-ene reaction of an alkoxyalkyne was achieved. The resulting synthesis was 18 steps in the longest linear sequence from either methyl acetoacetate or isobutyraldehyde.