环己醇,4-(三氟甲基)-,顺- | 142169-23-1

• 分子结构分类: 有机化合物 - 苯类化合物
• 中文名称: 环己醇,4-(三氟甲基)-,顺-
• 英文名称: 3-Vinyl-1,5-dihydro-3H-2,4-benzodioxepine
• 英文别名: 3-vinyl-1,5-dihydrobenzo[e][1,3]dioxepine；acrolein benzene-1,2-dimethanol acetal；3-ethenyl-1,5-dihydro-2,4-benzodioxepine
• CAS: 142169-23-1
• 化学式: C₁₁H₁₂O₂
• mdl: MFCD01318719
• 分子量: 176.215
• InChiKey: PQAODJNNLDUKSA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.272
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  环己醇,4-(三氟甲基)-,顺- 在 AD-mix-α 、 甲基磺酰胺 作用下， 以 水 、 叔丁醇 为溶剂， 反应 48.0h， 以93%的产率得到3-[(1R)-1,2-dihydroxyethyl]-1,5-dihydro-3H-2,4-benzodioxepine
  参考文献：
  名称：

  Synthesis of carbohydrates via tandem use of the osmium-catalyzed asymmetric dihydroxylation and enzyme-catalyzed aldol addition reactions

  摘要：

  A new strategy is described for the asymmetric synthesis of carbohydrate derivatives via the tandem use of the osmium-catalyzed asymmetric dihydroxylation (AD) and aldolase-catalyzed aldol addition reactions. Both D- and L-forms of fructose, 6-deoxy-galacto-2-heptulose, and 6-phenyl-galacto-2-hexulose were synthesized to illustrate this methodology.

  DOI：

  10.1021/ja00081a016
• 作为产物：
  描述：

  邻苯二甲酸二乙酯 在 lithium aluminium tetrahydride 、 对甲苯磺酸 、 原甲酸三甲酯 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 乙醚 为溶剂， 反应 5.0h， 生成 环己醇,4-(三氟甲基)-,顺-
  参考文献：
  名称：

  3-[(1S)-1,2-DIHYDROXYETHYL]-1,5-DIHYDRO-3H-2,4-BENZODIOXEPINE

  摘要：

  DOI：

  10.15227/orgsyn.073.0001

文献信息

• Synthesis of (+)-Discodermolide by Catalytic Stereoselective Borylation Reactions
  作者：Zhiyong Yu、Robert J. Ely、James P. Morken

  DOI：10.1002/anie.201405455

  日期：2014.9.1

  1990 and, to this day, remains a compelling synthesis target. Not only does the compound possess fascinating biological activity, but it also presents an opportunity to test current methods for chemical synthesis and provides an inspiration for new reaction development. A new synthesis of discodermolide employs a previously undisclosed stereoselective catalytic diene hydroboration and also establishes

  海洋天然产物 (+)-discodermolide 于 1990 年首次分离出来，至今仍是一个引人注目的合成目标。该化合物不仅具有令人着迷的生物活性，而且还为测试现有化学合成方法提供了机会，并为新反应的开发提供了灵感。 discodermolide 的新合成采用了先前未公开的立体选择性催化二烯硼氢化反应，并且还建立了手性烯醇化物烷基化的策略。此外，discodermolide 的这种合成提供了复杂分子合成中二烯不对称 1,4-二硼化和硼基化二烯-醛偶联的第一个例子。
• Oxidation of olefins by palladium(II). 18. Effect of reaction conditions, substrate structure and chiral ligand on the bimetallic palladium(II) catalyzed asymmetric chlorohydrin synthesis
  作者：Arab K El-Qisairi、Hanan A Qaseer、Patrick M Henry

  DOI：10.1016/s0022-328x(02)01580-2

  日期：2002.8

  The effect of electronic factors, solvent composition, identity of the chiral bidentate, and olefin structure on the yields and enantioselectivities of the asymmetric chlorohydrin synthesis were investigated. Electronic effects on the chlorohydrin reaction were tested by oxidation of phenyl allyl ether p-substituted by H, Cl, CH3O and CN. All species gave same similar yields and enantioselectivities

  研究了电子因素，溶剂组成，手性双齿的身份以及烯烃结构对不对称氯醇合成的收率和对映选择性的影响。通过H，Cl，CH 3 O和CN对-取代的苯基烯丙基醚的氧化，测试了对氯代醇反应的电子效应。所有物种都具有相同的相似产率和对映选择性，表明电子效应并不重要。改变THF-H 2 O混合物的溶剂组成表明，最佳溶剂混合物包含超过85％的THF。加入变异氯[Cl -]表明，为了获得高产率和％ee，添加的氯化物必须大于0.2M。在理想条件下，来自苯基烯丙基醚的氯醇的对映选择性大于90％ee。乙烯基乙酸，丙烯酸甲酯和反式-肉桂醛在通常的反应条件下不反应，而2-羟基-3-丁烯和乙酸烯丙酯的ee's低于苯基烯丙基醚。苯乙烯和α-甲基苯乙烯的反应速率相当，但后者的ee较低。（2，6-二异丙基）苯基烯丙基醚和2-羟基-3-丁烯给出高的ee，表明空间位阻不是主要因素。除DACH外，所有测试的手性桥联配体均给出令人满意的
• Optically active enantiomers of substituted glyceraldehydes or
  申请人：Massachusetts Institute of Technology

  公开号：US05162554A1

  公开（公告）日：1992-11-10

  Stable, optically active enantiomers of substituted glyceraldehydes or glycidaldehydes are synthesized by using osmium-catalyzed asymmetric dihydroxylation of an olefin which is a substituted 1,5-dihydro-3H-2,4-benzodioxepine. For example, the protected glyceraldehyde, 3-(1,2-dihydroxyethyl)-1,5-dihydro-3H-2,4-benzodioxepine and the protected glycidaldehyde, 3-(1,2-epoxyethyl)-1,5-dihydro-3H-2,4-benzodioxepine have been synthesized and the optical enantiomer has been recovered. In the synthetic and isolation methods, enantiomers with high enantiomeric excess are recovered from the mother liquor following a recrystallization step.

  使用奥斯米姆催化不对称二羟基化合成了取代甘油醛或甘氧醛的稳定、光学活性对映体，该催化反应的底物是取代的1,5-二氢-3H-2,4-苯并二氧杂环戊烯。例如，合成了保护的甘油醛，3-(1,2-二羟乙基)-1,5-二氢-3H-2,4-苯并二氧杂环戊烯和保护的甘氧醛，3-(1,2-环氧乙基)-1,5-二氢-3H-2,4-苯并二氧杂环戊烯，并回收了光学对映体。在合成和分离方法中，通过重新结晶步骤从母液中回收高对映体过量的对映体。
• Asymmetric dihydroxylation of acrolein acetals: synthesis of stable equivalents of Enantiopure glyceraldehyde and glycidaldehyde
  作者：Ryu Oi、K.Barry Sharpless

  DOI：10.1016/0040-4039(92)88149-y

  日期：1992.4

  Asymmetric dihydroxylation (ADH) of acrolein acetals afforded optically active glyceraldehyde equivalents. Enantiopure 3-(1,2-dihydroxyethyl)-1,5-dihydro-3H-2,4-benzodioxepine 3, a protected glyceraldehyde, was obtained from the corresponding acrolein acetal 2 by ADH and subsequent recrystallization. Enantiopure 3-(1,2-epoxyethyl)-1,5-dihydro-3H-2,4-benzodioxepine 5, a protected glycidaldehyde, was produced in two steps from 3.
• Enantioselective Hydroformylation of 1-Alkenes with Commercial Ph-BPE Ligand
  作者：Zhiyong Yu、Meredith S. Eno、Alexandra H. Annis、James P. Morken

  DOI：10.1021/acs.orglett.5b01421

  日期：2015.7.2

  A rhodium complex, in conjunction with commercially available Ph-BPE ligand, catalyzes the branch-selective asymmetric hydroformylation of 1-alkenes and rapidly generates alpha-chiral aldehydes. A wide range of terminal olefins Including 1-dodecene were examined, and all delivered high enantioselectivity (up to 98:2 er) as well as good branch:linear ratios (up to 15:1).