(Z)-2,2-dimethylhex-4-en-3-ol | 122053-44-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (Z)-2,2-dimethylhex-4-en-3-ol
• 英文别名: 2,2-dimethyl-hex-4c-en-3-ol
• CAS: 122053-44-5
• 化学式: C₈H₁₆O
• 分子量: 128.214
• InChiKey: LWNCLPPCYNKNEP-WAYWQWQTSA-N

物化性质

• 沸点：
  147.7±8.0 °C(Predicted)
• 密度：
  0.842±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  9
• 可旋转键数：
  2
• 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：

  (Z)-2,2-dimethylhex-4-en-3-ol 在 4-二甲氨基吡啶 、 氧气 、 tetraphenylporphyrin 、 三乙胺 、 三苯基膦 作用下， 以 四氯化碳 、 二氯甲烷 为溶剂， 反应 24.5h， 生成 3,4-diacetoxy-5,5-dimethylhex-1-ene
  参考文献：
  名称：

  Lipase-catalyzed kinetic resolution of threo -configured 1,2-diols: a comparative study of transesterification versus hydrolysis

  摘要：

  The kinetic resolution of the alpha,beta-unsaturated vicinal diols 3 has been investigated by irreversible transesterification in organic media and by hydrolysis of the corresponding diacetates 6 (Scheme 1). The best results were obtained in the hydrolysis of the diacetates with the lipase CAL-B from Candida antarctica as a catalyst. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(98)00043-3
• 作为产物：
  描述：

  顺式-1-溴-1-丙烯 、 特戊醛 在 碘 、 magnesium 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以61%的产率得到(Z)-2,2-dimethylhex-4-en-3-ol
  参考文献：
  名称：

  钯（II）催化的甲苯基甲苯磺酸氨基甲酸酯的氧化环化：范围，衍生化和机理方面

  摘要：

  据报道，高可用的氧化钯（II）催化（Wacker型）可轻易获得的烯丙基甲苯磺基氨基甲酸酯的环化反应。这种操作简单的催化反应可提供高收率和出色的非对映选择性（> 20：1）的甲苯磺酰基保护的乙烯基恶唑烷酮类化合物，它们是合成1,2-氨基醇的常见前体。已证明，化学计量的苯醌（BQ）以及有氧再氧化（分子氧）均适用于此转化。标题反应显示为通过整体反式进行烯烃的氨基缩钯反应，然后消除β-氢化物。此过程具有可扩展性，产品适用于一系列后续转化，例如：动力学拆分（KR）和氧化性Heck-，Wacker-和易位反应。

  DOI：

  10.1002/chem.201202359

文献信息

• Diastereoselectivity in the [2,3]-sigmatropic rearrangement of substituted allylic N,N-dialkylamidosulfoxylates. X-ray molecular structure of [(1′) S*, (S)S*]-(2′E)-4-[[3′-(4″-bromophenyl)-1′-methyl-2′-propenyl]sulfinyl]-morpholine
  作者：Jean-Bernard Baudin、Itka Bkouche-Waksman、Georges Hareau、Sylvestre A. Julia、Robert Lorne、Claudine Pascard

  DOI：10.1016/s0040-4020(01)82318-8

  日期：1991.8

  By the reaction with three N,N-dialkylamidosulfenyl chlorides 2 bearing representative sizes for the R groups on the nitrogen atom, several substituted secondary E or Z allylic alcohols (1a-h) have been converted into the corresponding pairs of diastereoisomeric allylic sulfinamides (3+-3′a-v), whose ratios have been determined by 1H NMR spectroscopy. Five cases of entirely diastereoselective [2,3]-sigmatropic

  通过与三个N，N-二烷基酰胺基亚磺酰氯2（在氮原子上具有代表性的R基团）反应，一些取代的仲E或Z烯丙基醇（1a-h）已转化为相应的非对映异构烯丙基亚磺酰胺（3 + -3'av），其比例已通过1 H NMR光谱测定。已经观察到五例完全非对映选择性[2,3]-σ重排的情况。
• Regio- and Diastereoselective Catalytic Epoxidation of Acyclic Allylic Alcohols with Methyltrioxorhenium:  A Mechanistic Comparison with Metal (Peroxy and Peroxo Complexes) and Nonmetal (Peracids and Dioxirane) Oxidants
  作者：Waldemar Adam、Catherine M. Mitchell、Chantu R. Saha-Möller

  DOI：10.1021/jo9902289

  日期：1999.5.1

  Geraniol and its 1-methyl derivative (regiochemical probes) and a set of methyl- and tert-butyl-substituted chiral allylic alcohols (stereochemical probes) have been used to elucidate the mechanism of the MTO-catalyzed epoxidation of allylic alcohols. The regiochemical probes are preferentially epoxidized at the unfunctionalized double bond by these MTO-based oxidants, which establishes that MTO/UHP

  香叶醇及其1-甲基衍生物（区域化学探针）和一组甲基和叔丁基取代的手性烯丙基醇（立体化学探针）已用于阐明MTO催化的烯丙基醇环氧化的机理。区域化学探针优先通过这些基于MTO的氧化剂在未官能化的双键上环氧化，从而确定MTO / UHP和MTO / H（2）O（2）/吡啶主要通过氢键起作用。与过渡金属氧化剂VO（acac）（2）/ t-BuOOH，Mo（CO）（6）/ t-BuOOH，MoO（2）[PhCON（Ph ）O]（2）/ t-BuOOH，MoO（O（2））[PhCON（Ph）O]（2）和H（2）WO（4）/ H（2）O（2）。对于立体化学探针，非对映选择性数据显示MTO催化系统（MTO / UHP和MTO / H（2）O（2）/吡啶）与过水合物型氧化剂Ti-beta / H（2）O（2）和过酸m-CPBA。通过1，3-烯丙基应变的构象控制导致高的苏非对映选择性，其中羟基官能度和and催
• Hydroxy-directed regio-diastereoselective ene reaction of singlet oxygen with chiral allylic alcohols
  作者：Waldemar Adam、Bernd Nestler

  DOI：10.1021/ja00065a013

  日期：1993.6

  The photooxygenation of chiral allylic alcohols 1a, (Z)-1f-k, ethers 1b-d, and acetate 1e gave the corresponding hydroperoxy homoallylic alcohols and derivatives 2 through the ene reaction with singlet oxygen. While the reaction of the acetate 1e proceeded erythro-diastereoselectively as a result of the classical cis effect, for the allylic alcohols 1a and (Z)-1f-k, in which an alkyl group is located

  手性烯丙醇 1a、(Z)-1f-k、醚 1b-d 和乙酸酯 1e 的光氧化反应通过与单线态氧的烯反应得到相应的氢过氧高烯丙醇和衍生物 2。由于经典的顺式效应，乙酸酯 1e 的反应以赤型非对映选择性进行，对于烯丙醇 1a 和 (Z)-1f-k，其中烷基位于带羟基的取代基的顺式，高观察到threo选择性。这一发现可以通过立体中心的亲核羟基官能团与进入的亲电子单线态氧亲烯体的配位来解释
• Hydroxy-directed diastereoselective ene reaction of triazolinediones with chiral allylic alcohols
  作者：Waldemar Adam、Bernd Nestler、Aurelia Pastor、Thomas Wirth

  DOI：10.1016/s0040-4039(98)00222-6

  日期：1998.4

  The ene reaction of the N-methyltriazolidinone (MTAD) with the allylic alcohols 1a-e afforded the corresponding urazoles 2 in high threo diastereoselectivity (Scheme 1). These results are mechanistically explained in terms of an attractive hydrogen-bonding interaction between the enophile and the allylic hydroxy functionality in the threo transition state, which is favored on account of minimal 1,3-allylic

  所述的烯反应Ñ -methyltriazolidinone（MTAD）与烯丙基醇1A-E ，得到相应的urazoles 2在高苏式非对映选择性（方案1）。这些结果用苏氨酸过渡态中的亲和体与烯丙基羟基官能团之间的有吸引力的氢键相互作用来机械地解释，这由于最小的1,3-烯丙基应变而受到青睐。所述苏当烯丙基羟基官能团被掩蔽非对映选择性的完全丧失。结果与先前在单线态氧烯反应中建立的羟基导向作用相似。
• Diastereoselective Catalytic Epoxidation of Chiral Allylic Alcohols by the TS-1 and Ti-β Zeolites:  Evidence for a Hydrogen-Bonded, Peroxy-Type Loaded Complex as Oxidizing Species
  作者：Waldemar Adam、Avelino Corma、T. Indrasena Reddy、Michael Renz

  DOI：10.1021/jo970364i

  日期：1997.5.1

  The similar diastereoselectivities as for peracids implicate a pentacoordinated metal peroxy species in the epoxidation of chiral allylic alcohols by the titanium-containing zeolites TS-1 and Ti-beta. In the loaded complex, the allylic alcohol substrate is fixed through hydrogen bonding to the metal center, with A(1,3) strain as the dominant conformational feature. By comparison of the diastereoselectivities to those for VO(acac)(2)/t-BuOOH, we exclude a peroxy-type complex with direct coordination of the allylic alcohol to the titanium center by means of metal-alcoholate bonding. Neither does a peroxo-type titanium complex apply, as confirmed by comparing the diastereoselectivities with those observed for dioxiranes. With the help of tert-butyl-substituted allylic alcohols as substrates, which are not epoxidized by the TS-1 but by the Ti-beta catalyst, it was unequivocally confirmed that the oxidation occurs inside of the zeolite and not on the outer surface.