trans-2-methyl-5-hepten-2-ol

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: trans-2-methyl-5-hepten-2-ol
• 英文别名: (E)-2-methyl-5-hepten-2-ol；(E)-2-methylhept-5-en-2-ol
• 化学式: C₈H₁₆O
• 分子量: 128.214
• InChiKey: BZBFCIFBIAKGGK-SNAWJCMRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  乙基溴化镁 、 trans-2-methyl-5-hepten-2-ol 在 titanium(IV) isopropylate 作用下， 以 乙醚 为溶剂， 反应 1.0h， 生成 3,7-二甲基-辛烯-2-醇
  参考文献：
  名称：

  Reductive ethylation of homoallyl alcohols with a disubstituted double bond with ethylmagnesium bromide in the presence of titanium(IV) isopropoxide

  摘要：

  Homoallyl and bishomoallyl alcohols with a disubstituted double bond treated with ethylmagnesium bromide in the presence of titanium(IV) isopropoxide are converted into the products of a reductive ethylation of the olefin fragment. Under similar conditions esters of beta,gamma-unsaturated carboxylic acids undergo a successive cyclopropanation of the ester group and reductive ethylation of the double carbon-carbon bond and yield 1-(3-ethylalkyl)cyclopropanols. The features of the observed reactions are explained in the framework of the carbometallation mechanism of the double carbon-carbon bond by the action of dialkoxytitanacyclopropane reagents.

  DOI：

  10.1134/s1070428006050034

文献信息

• Palladium-Catalyzed Synthesis of 2,1‘-Disubstituted Tetrahydrofurans from γ-Hydroxy Internal Alkenes. Evidence for Alkene Insertion into a Pd−O Bond and Stereochemical Scrambling via β-Hydride Elimination
  作者：Michael B. Hay、John P. Wolfe

  DOI：10.1021/ja054754v

  日期：2005.11.30

  diastereoselectivity in reactions of acyclic internal alkene substrates likely derives from a series of reversible β-hydride elimination and σ-bond rotation processes that occur following a rare intramolecular alkene syn-insertion into an intermediate Pd(Ar)(OR) complex. In addition, these studies shed light on the chemoselectivity of insertion, suggesting that the alkene inserts into the Pd−O bond in preference

  γ-羟基内部无环烯烃与芳基溴化物的钯催化反应以良好的收率提供 2,1'-二取代的四氢呋喃，非对映选择性为 3-5:1。带有内部环状烯烃的底物的类似转化以良好的收率提供稠合的双环和螺环四氢呋喃衍生物，并具有出色的非对映选择性 (>20:1)。一系列氘标记实验表明，非环状内部烯烃底物反应中适度的非对映选择性的起源可能源于一系列可逆的 β-氢化物消除和 σ-键旋转过程，这些过程发生在罕见的分子内烯烃合成插入到中间体 Pd(Ar)(OR) 络合物。此外，这些研究阐明了插入的化学选择性，
• Stereoselective Synthesis of Tetrahydrofurans via the Palladium-Catalyzed Reaction of Aryl Bromides with γ-Hydroxy Alkenes:  Evidence for an Unusual Intramolecular Olefin Insertion into a Pd(Ar)(OR) Intermediate
  作者：John P. Wolfe、Michael A. Rossi

  DOI：10.1021/ja0394838

  日期：2004.2.1

  A new, stereoselective method for the synthesis of substituted tetrahydrofurans from gamma-hydroxy alkenes that forms both a C-C and a C-O bond with diastereoselectivities of up to >20:1 is described. Initial mechanistic studies that suggest the reactions proceed via the intramolecular insertion of an olefin into a Pd(Ar)(OR) intermediate are discussed.

  描述了一种新的立体选择性方法，用于从 γ-羟基烯烃合成取代的四氢呋喃，该方法形成 CC 和 CO 键，非对映选择性高达 > 20:1。初步的机理研究表明反应是通过烯烃分子内插入 Pd(Ar)(OR) 中间体进行的。
• 10,1021/011001472
  作者：Ward, Amanda F.、Wolfe, John P.

  DOI：10,1021/011001472

  日期：——
• Borenium Ion Catalyzed Hydroboration of Alkenes with N-Heterocyclic Carbene-Boranes
  作者：Aleksandrs Prokofjevs、Anne Boussonnière、Linfeng Li、Hélène Bonin、Emmanuel Lacôte、Dennis P. Curran、Edwin Vedejs

  DOI：10.1021/ja305061c

  日期：2012.7.25

  Treatment of alkenes such as 3-hexene, 3-octene, and 1-cyclohexyl-1-butene with the N-heterocyclic carbene (NHC)-derived borane 2 and catalytic HNTf2 (Tf = trifluoromethanesulfonyl (CF3SO2)) effects hydroboration at room temperature. With 3-hexene, surprisingly facile migration of the boron atom from C(3) of the hexyl group to C(2) was observed over a time scale of minutes to hours. Oxidative workup gave a mixture of alcohols containing 2-hexanol as the major product. A similar preference for the C(2) alcohol was observed after oxidative workup of the 3-octene and 1-cyclohexyl-1-butene hydroborations. NHC-borenium cations (or functional equivalents) are postulated as the species that accomplish the hydroborations, and the C(2) selective migrations are attributed to the four center interconversion of borenium cations with cationic NHC-borane-olefin pi-complexes.
• ANTIBIOTIC 107891, ITS FACTORS A1 AND A2, PHARMACEUTICALLY ACCEPTABLE SALTS AND COMPOSITIONS, AND USE THEREOF
  申请人：Vicuron Pharmaceuticals, Inc.

  公开号：EP1855705A1

  公开（公告）日：2007-11-21