5-Methyl-5-hexen-1-yn-3-ol | 92975-51-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-Methyl-5-hexen-1-yn-3-ol
• 英文别名: 5-methylhex-5-en-1-yn-3-ol
• CAS: 92975-51-4
• 化学式: C₇H₁₀O
• 分子量: 110.156
• InChiKey: XKKTUTJEXYTHNY-UHFFFAOYSA-N

物化性质

• 沸点：
  170.2±20.0 °C(Predicted)
• 密度：
  0.913±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  5-Methyl-5-hexen-1-yn-3-ol 在 4-二甲氨基吡啶 、 正丁基锂 、 三乙胺 作用下， 生成 4-[tert-butyl(dimethyl)silyl]oxy-6-methylhept-6-en-2-yn-1-ol
  参考文献：
  名称：

  Radical cyclisation of bromomethyldimethylsilyl propynyl ethers; serial radical cyclisations leading to a hydrindene framework from an acyclic substrate, stereoselectively

  摘要：

  制备了4-溴甲基二甲基硅氧基-2,8,8-三甲基癸-1-烯-5,9-二炔11，通过三个连续的5-外二聚体、5-外三聚体和6-外二聚体自由基过程，其自由基环化导致了一种氢化茚框架13的立体选择性合成。

  DOI：

  10.1039/c39940000461
• 作为产物：
  描述：

  5-Methyl-1-(trimethylsilyl)-5-hexen-1-yn-3-ol 在 potassium fluoride 作用下， 以 二甲基亚砜 为溶剂， 反应 1.0h， 以100%的产率得到5-Methyl-5-hexen-1-yn-3-ol
  参考文献：
  名称：

  Radical cyclization of (bromomethyl)dimethylsilyl propargyl ethers. Regio-, chemo- and stereoselectivity.

  摘要：

  Radical cyclization of (bromomethyl)dimethylsilyl propargyl ether derivatives 1 is a powerful reaction with a high degree of regio-, chemo-, and stereoselectivity. Trisubstituted olefins 3, cyclopentene derivatives 5, and diquinane system 7j are obtained in good yields by a judicious choice of unsaturated substituents. Triquinane frameworks could be obtained stereoselectively from a suitable acyclic substrate of type 1 in a one-pot reaction. First attempts have not yet allowed us to aim at this goal due to interesting (1,5) hydrogen transfers. Moreover, we have intercepted, for the first time, the alpha-cyclopropyl radical which is involved in the Stork-Beckwith mechanism of the 5-versus 6-membered ring formation in the vinyl radical cyclization.

  DOI：

  10.1021/jo00037a026

文献信息

• PtCl₂-Catalyzed Cycloisomerizations of 5-En-1-yn-3-ol Systems
  作者：Youssef Harrak、Christophe Blaszykowski、Matthieu Bernard、Kevin Cariou、Emily Mainetti、Virginie Mouriès、Anne-Lise Dhimane、Louis Fensterbank、Max Malacria

  DOI：10.1021/ja0474695

  日期：2004.7.1

  5-En-1-yn-3-ol substrates bearing a free hydroxyl group or an acyl group are highly versatile partners for PtCl2-catalyzed cycloisomerizations. Electrophilic activation of the alkyne moiety triggers at wish a hydride or an O-acyl migration yielding at the end to regioisomeric keto derivatives. The efficient preparation of Sabina ketone, an important monoterpene precursor, has been worked out.

  带有游离羟基或酰基的 5-En-1-yn-3-ol 底物是 PtCl2 催化的环异构化的通用伙伴。炔烃部分的亲电活化可触发氢化物或 O-酰基迁移，最终产生区域异构酮衍生物。已经研究出重要的单萜前体Sabina酮的有效制备。
• Platinum(II) Chloride Catalyzed Cycloisomerizations of 1,5-Enynes
  作者：Anne-Lise Dhimane、Louis Fensterbank、Max Malacria、Christophe Blaszykowski、Youssef Harrak、Célia Brancour、Kimitaka Nakama

  DOI：10.1055/s-2007-983736

  日期：2007.7

  1,5-Enynes are highly reactive under PtCl2 catalysis and give a range of [3.1.0] bicyclic skeletons. The scope and limitations of this process are presented. Regioisomeric keto derivatives are obtained depending upon the nature of the oxygenated substituent at the propargylic position of the starting substrate.

  1,5-烯炔在PtCl2催化下具有高度的反应活性，并且可以生成一系列[3.1.0]双环骨架结构。本文介绍了该过程的范围和局限性。根据起始原料丙炔位上含氧化取代基的性质，可以获得不同的区域异构酮衍生物。
• Gold‐ vs. Platinum‐Catalyzed Polycyclizations by <i>O</i> ‐Acyl Migration. Solvent‐Free Reactions
  作者：Xavier Moreau、Jean‐Philippe Goddard、Matthieu Bernard、Gilles Lemière、Juan Manuel López‐Romero、Emily Mainetti、Nicolas Marion、Virginie Mouriès、Serge Thorimbert、Louis Fensterbank、Max Malacria

  DOI：10.1002/adsc.200700356

  日期：2008.1.4

  Polycyclic derivatives incorporating a cyclopropyl group have been efficiently synthesized from propargyl acetates using platinum(II), gold(I) and gold(III) catalysis. These reactions which are also viable for the preparation of medium-sized rings, proceed with a complete diastereocontrol and can also be run in neat conditions.

  使用铂（II），金（I）和金（III）催化，可从乙酸炔丙酯高效合成具有环丙基的多环衍生物。这些反应对于制备中型环也是可行的，可以进行完全的非对映控制，也可以在纯净条件下进行。
• Silver mediated acetylenic oxy cope rearrangement
  作者：Norbert Bluthe、Jacques Gore、Max Malacria

  DOI：10.1016/s0040-4020(01)87352-x

  日期：1986.1
• Transposition d'oxy-cope d'hexene-5 yne-1 ols-3 assistee par le triflate d'argent
  作者：Norbert Bluthe、Max Malacria、Jacques Gore

  DOI：10.1016/s0040-4039(01)81313-7

  日期：1984.1