(3S,4R)-5-Methylhex-1-ene-3,4-diol | 181714-87-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3S,4R)-5-Methylhex-1-ene-3,4-diol
• CAS: 181714-87-4
• 化学式: C₇H₁₄O₂
• 分子量: 130.187
• InChiKey: WTRPIFJNKQUEEO-NKWVEPMBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  丙酮 、 (3S,4R)-5-Methylhex-1-ene-3,4-diol 在 对甲苯磺酸 作用下， 以 四氯化碳 、 水 、 乙腈 为溶剂， 反应 30.0h， 以53%的产率得到(2R,3R)-2,3-Isopropylidenedioxy-4-methylpentanoic acid
  参考文献：
  名称：

  不对称二乙烯基甲醇无尖锐不对称环氧化的研究

  摘要：

  外消旋不对称二乙烯基甲醇rac -13在Sharpless不对称环氧化条件下，使用化学计量的四异丙氧基钛[Ti（OP i）4]，D -（-）-酒石酸二异丙酯（DIPT）和叔丁基氢过氧化物（TBHP）进行反应R -14和R -15的收率分别为41％和43％，ee均> 99％，其中动力学拆分和随后的环氧化反应均以完全区域选择性和非对映选择性的方式进行。

  DOI：

  10.1039/p19960001729
• 作为产物：
  描述：

  (S)-1-((S)-3,3-Dimethyl-oxiranyl)-prop-2-en-1-ol 在 二异丁基氢化铝 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 2.0h， 以50%的产率得到(3S,4R)-5-Methylhex-1-ene-3,4-diol
  参考文献：
  名称：

  不对称二乙烯基甲醇无尖锐不对称环氧化的研究

  摘要：

  外消旋不对称二乙烯基甲醇rac -13在Sharpless不对称环氧化条件下，使用化学计量的四异丙氧基钛[Ti（OP i）4]，D -（-）-酒石酸二异丙酯（DIPT）和叔丁基氢过氧化物（TBHP）进行反应R -14和R -15的收率分别为41％和43％，ee均> 99％，其中动力学拆分和随后的环氧化反应均以完全区域选择性和非对映选择性的方式进行。

  DOI：

  10.1039/p19960001729

文献信息

• Stereoselective acyclic synthesis via allylmetals: vicinal diols from γ-alkoxyallylaluminium compounds and aldehydes or ketones
  作者：Masato Koreeda、Yoshio Tanaka

  DOI：10.1039/c39820000845

  日期：——

  The reaction of in situ generated γ-alkoxyallylaluminium compounds with aldehydes or ketones at –78 °C leads to the highly diastereoselective formation of mono-protected vicinal diols; the precursor to exo-brevicomin was efficiently synthesised using this method.

  的反应原位生成的γ -alkoxyallylaluminium化合物与在-78℃下通向高度非对映形成单保护邻二醇的醛或酮; 用这种方法有效地合成了exo- brevicomin的前体。
• Horseradish Peroxidase-Catalyzed Enantioselective Reduction of Racemic Hydroperoxy Homoallylic Alcohols:  A Novel Enzymatic Method for the Preparation of Optically Active, Unsaturated Diols and Hydroperoxy Alcohols
  作者：Waldemar Adam、Michael Lazarus、Ute Hoch、Marion N. Korb、Chantu R. Saha-Möller、Peter Schreier

  DOI：10.1021/jo980028h

  日期：1998.9.1

  The kinetic resolution of chiral diastereomeric hydroperoxy homoallylic alcohols 1 by horseradish peroxidase-catalyzed asymmetric reduction affords the optically active (R,R) or (R,S) allylic diols 2 and (S,S) or (S,R) hydroperoxy homoallylic alcohols 1 in high enantiomeric excess (up to 99%).

  辣根过氧化物酶催化的不对称还原动力学拆分手性非对映体氢过氧均丙醇1，提供光学活性（R，R）或（R，S）烯丙基二醇2和（S，S）或（S，R）氢过氧均丙醇高对映体过量（高达99％）中为1。
• 3-Bromozinc Propenyl Esters:  An Experimental and Theoretical Study of the Unique Stereocrossover Observed in Their Addition to Aromatic and Aliphatic Aldehydes
  作者：A. Bottoni、M. Lombardo、G. P. Miscione、J. B. Pujol Algué、C. Trombini

  DOI：10.1021/jo701661z

  日期：2008.1.1

  [GRAPHICS]We report the results of a combined experimental and theoretical study on the reaction of 3-bromopropenyl acetate in the presence of zinc with three different aldehydes (i.e., benzaldehyde, 2-methylpropanal, and cyclohexanecarboxaldehyde). A 80% de in favor of the anti product has been experimentally observed. with both saturated aldehydes, while for benzaldehyde, a 1:1 synlanti ratio has been found. DFT computations show the existence of three eta(1)-allylic organozinc complexes [gamma-(Z)-5a, gamma-(E)-5a, and alpha-5a], very close in energy. Only gamma-(Z)-5a and gamma-(E)-5a lead to the observed product. The computational investigation of the reaction of these allylic organozinc complexes with benzaldehyde and 2-methylpropanal demonstrates in both cases the existence of two competitive reaction paths leading to the syn and anti adducts, respectively. An anti preference has been found for 2-methylpropanal with both gamma-(Z)-5a and gamma-(E)-5a species (a diastereoselectivity larger than 80% is predicted), in agreement with the experiment. With benzaldehyde, while the reaction of gamma-(Z)-5a retains an anti-stereopreference (de = 70%), that involving gamma-(E)-5a is characterized by two degenerate transition states. In this case, the agreement between computations and experiments would be satisfactory under the assumption that the initial oxidative addition affords the gamma-(E)-5a zinc complex only. Additional MP2 computations have demonstrated that pi-stacking interactions can play a significant role in determining the relative energy of the transition states leading to the syn and anti products.
• Horseradish peroxidase (HRP)-catalysed enantioselective reduction of racemic hydroperoxy homoallylic alcohols: a novel enzymatic method for the preparation of optically active, unsaturated diols and hydroperoxy alcohols
  作者：Waldemar Adam、Ute Hoch、Hans-Ulrich Humpf、Chantu R. Saha-Möller、Peter Schreier

  DOI：10.1039/cc9960002701

  日期：——

  The kinetic resolution of chiral diastereoisomeric hydroperoxy homoallylic alcohols by horseradish peroxidase (HRP)-catalysed asymmetric reduction affords the optically active (R,R) or (R,S) allylic diols and (S,S) or (S,R) hydroperoxy homoallylic alcohols in high enantiomeric excess (up to 99%).
• Studies on the sharpless asymmetric epoxidation of unsymmetrical divinylmethanols
  作者：Toshio Honda、Hirotake Mizutani、Kazuo Kanai

  DOI：10.1039/p19960001729

  日期：——

  A reaction of racemic unsymmetrical divinylmethanol rac-13 under the Sharpless asymmetric epoxidation conditions using stoichiometric amounts of titanium tetraisopropoxide [Ti(OPi)4], D-(–)-diisopropyl tartrate (DIPT) and tert-butyl hydroperoxide (TBHP) afforded R-14 and R-15 in 41 and 43% yield, each with > 99%ee, respectively, where the kinetic resolution and subsequent epoxidation had proceeded

  外消旋不对称二乙烯基甲醇rac -13在Sharpless不对称环氧化条件下，使用化学计量的四异丙氧基钛[Ti（OP i）4]，D -（-）-酒石酸二异丙酯（DIPT）和叔丁基氢过氧化物（TBHP）进行反应R -14和R -15的收率分别为41％和43％，ee均> 99％，其中动力学拆分和随后的环氧化反应均以完全区域选择性和非对映选择性的方式进行。