5-methyl-4-hexen-3-ol

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-methyl-4-hexen-3-ol
• 英文别名: (S)-5-methylhex-4-en-3-ol；(3S)-5-methylhex-4-en-3-ol
• 化学式: C₇H₁₄O
• 分子量: 114.188
• InChiKey: SMKXEJCDVREDQY-ZETCQYMHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 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-4-hexen-3-ol 在 氧气 、 tetraphenylporphyrin 作用下， 以 二氯甲烷 为溶剂， 反应 8.0h， 生成 4-hydroperoxy-5-methylhex-5-en-3-ol 、 (3S,4S)-4-hydroperoxy-5-methylhex-5-en-3-ol
  参考文献：
  名称：

  单线态氧与手性烯丙基醇的非对映选择性申克反应；获得对映体富集的1,2,4-三恶烷

  摘要：

  一系列抗疟疾手性1,2,4-三恶烷（的1 - 8）在高对映体纯度合成。的不对称加成的R 2的Zn试剂由（+）催化的3-甲基-2-丁烯醛- MIB或（ - ） - MIB，得到手性烯丙基醇的两个对映异构体9 - 11（90-98％ee）的，这是进行非对映选择性光氧化在四苯基的存在（TPP），得到（- [R ，- [R ）-苏型-或（小号，小号） -苏-β-氢过氧醇（12 - 14）。β-氢过氧醇的反应（12– 14）用不同的环酮生产旋光三恶烷1 – 8。

  DOI：

  10.1016/j.tet.2009.08.020
• 作为产物：
  描述：

  3-甲基-2-丁烯醛 、 diethylzinc 在 (1R,2S,3R,4S)-1,7,7-三甲基-3-(4-吗啉基)双环[2.2.1]庚烷-2-醇 、 水 、 氯化铵 作用下， 以 正己烷 为溶剂， 反应 4.0h， 以55%的产率得到5-methyl-4-hexen-3-ol
  参考文献：
  名称：

  单线态氧与手性烯丙基醇的非对映选择性申克反应；获得对映体富集的1,2,4-三恶烷

  摘要：

  一系列抗疟疾手性1,2,4-三恶烷（的1 - 8）在高对映体纯度合成。的不对称加成的R 2的Zn试剂由（+）催化的3-甲基-2-丁烯醛- MIB或（ - ） - MIB，得到手性烯丙基醇的两个对映异构体9 - 11（90-98％ee）的，这是进行非对映选择性光氧化在四苯基的存在（TPP），得到（- [R ，- [R ）-苏型-或（小号，小号） -苏-β-氢过氧醇（12 - 14）。β-氢过氧醇的反应（12– 14）用不同的环酮生产旋光三恶烷1 – 8。

  DOI：

  10.1016/j.tet.2009.08.020

文献信息

• Highly Enantio- and Diastereoselective One-Pot Synthesis of Acyclic Epoxy Alcohols with Three Contiguous Stereocenters
  作者：Alice E. Lurain、Aaron Maestri、Ann Rowley Kelly、Patrick J. Carroll、Patrick J. Walsh

  DOI：10.1021/ja046750g

  日期：2004.10.1

  Two highly enantio- and diastereoselective one-pot procedures for the synthesis of epoxy alcohols with up to three contiguous stereocenters are reported. Route one involves asymmetric addition of an alkylzinc reagent to an enal followed by diastereoselective epoxidation. Route two entails asymmetric vinylation of an aldehyde with divinylzinc reagents and subsequent diastereoselective epoxidation. The

  报道了用于合成具有多达三个连续立体中心的环氧醇的两种高度对映选择性和非对映选择性的一锅法。途径一涉及将烷基锌试剂不对称加成到烯醛，然后进行非对映选择性环氧化。路线二需要醛与二乙烯基锌试剂的不对称乙烯基化和随后的非对映选择性环氧化。用于环氧化的氧化剂是通过将烯丙基醇盐中间体和剩余的有机锌试剂暴露于双氧而产生的。在加入催化性四异丙醇钛后，定向环氧化以良好到极好的收率产生环氧醇。
• [EN] PROCESSES FOR HIGHLY ENANTIO-AND DIASTEREOSELECTIVE SYNTHESIS OF ACYCLIC EPOXY ALCOHOLS AND ALLYLIC EPOXY ALCOHOLS<br/>[FR] PROCEDES DE SYNTHESE HAUTEMENT ENANTIOSELECTIVE ET DIASTEREOSELECTIVE D'EPOXYALCOOLS ACYCLIQUES ET D'EPOXYALCOOLS ALLYLIQUES
  申请人：UNIV PENNSYLVANIA

  公开号：WO2005087755A1

  公开（公告）日：2005-09-22

  The inventive subject matter relates to novel processes for making an epoxy alcohol from an aldehyde, comprising the steps of: (a) adding (i) an organozinc compound or (ii) divinylzinc compound and an diorganozinc compound to said aldehyde in the presence of a first catalyst to form an allylic alkoxide compound; and (b) epoxidizing said allylic alkoxide compound in the presence of an oxidant and a second catalyst.

  发明主题涉及从醛制备环氧醇的新颖工艺，包括以下步骤：(a) 在第一催化剂的存在下，向所述醛中添加(i)有机锌化合物或(ii)二乙烯基锌化合物和二有机锌化合物，以形成烯丙基烷氧基化合物；以及(b) 在氧化剂和第二催化剂的存在下，将所述烯丙基烷氧基化合物环氧化。
• Processes for Highly Enantio- and Diastereoselective Synthesis of Acyclic Epoxy Alcohols and Allylic Epoxy Alcohols
  申请人：Walsh Patrick

  公开号：US20090163728A1

  公开（公告）日：2009-06-25

  The inventive subject matter relates to novel processes for making an epoxy alcohol from an aldehyde, comprising the steps of: (a) adding (i) an organozinc compound or (ii) divinylzinc compound and an diorganozinc compound to said aldehyde in the presence of a first catalyst to form an allylic alkoxide compound; and (b) epoxidizing said allylic alkoxide compound in the presence of an oxidant and a second catalyst.

  本发明涉及一种从醛制备环氧醇的新工艺，包括以下步骤：(a)在第一催化剂的存在下向所述醛中加入(i)有机锌化合物或(ii)二乙烯基锌化合物和二有机锌化合物，以形成烯丙氧化物化合物；(b)在氧化剂和第二催化剂的存在下使烯丙氧化物化合物环氧化。
• From Highly Enantioselective Monomeric Catalysts to Highly Enantioselective Polymeric Catalysts:  Application of Rigid and Sterically Regular Chiral Binaphthyl Polymers to the Asymmetric Synthesis of Chiral Secondary Alcohols
  作者：Wei-Sheng Huang、Qiao-Sheng Hu、Lin Pu

  DOI：10.1021/jo990992v

  日期：1999.10.1

  A 1,1'-binaphthyl-based polymeric chiral catalyst with the most general enantioselectivity for the alkylzinc addition to a broad range of aldehydes has been obtained. This polymer can be easily recovered, and the recycled polymer shows the same catalytic properties as the original polymer. A highly enantioselective catalytic diphenylzinc addition to aldehydes has also been achieved by using the chiral binaphthyl monomer and polymer catalysts. Particularly, the excellent enantioselectivity observed for the addition of diphenylzinc to aromatic aldehydes allows the preparation of optically active diaryl carbinols that are synthetically useful but difficult to access by asymmetric catalysis. A novel asymmetric reduction of ketones catalyzed by the mono- and polybinaphthyl zinc complexes has been discovered. Our work on the asymmetric organozinc addition to aldehydes and the asymmetric reduction of ketones catalyzed by the zinc complexes of chiral binaphthyl monomer (R)-12 and polybinaphthyl (R)-43 has not only provided new methods to prepare optically active secondary alcohols but also demonstrated that incorporation of an enantioselective monomeric catalyst into a rigid and sterically regular polymer structure could almost completely preserve the catalytic properties of the monomeric catalyst. This strategy may find general application in converting existing highly enantioselective monomer catalysts into polymer catalysts of similar enantioselectivity provided that the catalytically active species of the monomer catalysts contain only the monomeric units rather than the aggregates of the monomers. By using this strategy, it is possible to overcame the drawbacks associated with the traditional approach to preparing polymeric chiral catalysts where the microenvironments of the catalytic sites in the polymers are often significantly altered from those in the monomeric catalysts due to the flexible and sterically irregular polymer chains.
• A Highly General Catalyst for the Enantioselective Reaction of Aldehydes with Diethylzinc
  作者：Wei-Sheng Huang、Qiao-Sheng Hu、Lin Pu

  DOI：10.1021/jo971985e

  日期：1998.3.1