trans-2-hexenyl tosylate | 205882-94-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: trans-2-hexenyl tosylate
• 英文别名: (E)-2-hexenyl tosylate；toluene-4-sulfonic acid (E)-hex-2-en-1-yl ester；[(E)-hex-2-enyl] 4-methylbenzenesulfonate
• CAS: 205882-94-6
• 化学式: C₁₃H₁₈O₃S
• 分子量: 254.35
• InChiKey: FPZCXYJLPHHXAL-AATRIKPKSA-N

物化性质

• 沸点：
  365.3±21.0 °C(Predicted)
• 密度：
  1.105±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  trans-2-hexenyl tosylate 在 三甲基铝 、 对甲苯磺酸 作用下， 以 甲苯 为溶剂， 反应 32.0h， 生成 [2,2-Dimethyl-3-vinyl-hex-(E)-ylidene]-isobutyl-amine
  参考文献：
  名称：

  Studies of the regiospecific 3-aza-Cope rearrangement promoted by electrophilic reagents

  摘要：

  The 3-aza-Cope rearrangement of N-alkyl-N-allyl enamine substrates, which required temperatures of 250 250-degrees-C to proceed thermally, was promoted at 111-degrees-C in the presence of electrophilic reagents such as HCl (0.5 equiv) TiCl4 (0.2 equiv), AlMe3 (1.2 equiv), or (ArO)2AlMe (1.2 equiv). In order to probe the regioselectivity of this accelerated carbon-carbon bond forming process under these reaction conditions, several enamine substrates were prepared from both isobutyraldehyde and cyclohexanone. Each substrate used in these studies was prepared having an unsymmetrical N-allylic group, substituted with either an alkyl or phenyl substituent at the 4 or 6 position of the 3-aza-Cope framework. In all cam examined, reaction acceleration by the electrophilic reagent produced regiospecific [3,3] rearrangement to the corresponding products resulting from [1,3] rearrangement were not observed. Hydride reduction of the resulting imines generated the delta,epsilon-unsaturated amines in 55-94% overall yield in the three-step condensation-rearrangement-reduction process from the secondary allylamine.

  DOI：

  10.1021/jo00052a037
• 作为产物：
  描述：

  反式-2-已烯-1-醇 、 对甲苯磺酰氯 在 氢氧化钾 作用下， 生成 trans-2-hexenyl tosylate
  参考文献：
  名称：

  钯催化烯丙基甲苯磺酸酯和炔烃羰基环加成环戊烯酮

  摘要：

  甲苯磺酸烯丙酯和炔烃的羰基化环加成在钯催化剂存在下进行，得到一系列环戊烯酮。在甲醇存在下，五组分偶联反应得到甲基环戊烯基乙酸酯，而在没有甲醇的情况下，由六组分形成（环戊烯酰基亚甲基）呋喃酮。发现甲苯磺酸烯丙酯对这些反应是必不可少的，因为乙酸烯丙酯和烯丙基溴被证明是无效的。

  DOI：

  10.1055/s-2006-942538

文献信息

• Benzannulation from Alkynes and Allyl Tosylates via a π-Allylpalladium Intermediate
  作者：Naofumi Tsukada、Shuichi Sugawara、Yoshio Inoue

  DOI：10.1021/ol991406n

  日期：2000.3.1

  [reaction: see text] Allyl tosylate is a good allyl source for a novel palladium-catalyzed benzannulation that affords polysubstituted benzenes from 1 mol of an allyl compound and 2 mol of internal alkynes. Using triphenyl phosphite as a ligand, the reaction with terminal alkynes gave trisubstituted benzenes regioselectively.

  [反应：参见正文]甲苯磺酸烯丙基酯是新型钯催化的苯环烷基化物的良好烯丙基来源，该苯环烷基化物由1摩尔的烯丙基化合物和2摩尔的内部炔烃提供多取代的苯。使用亚磷酸三苯酯作为配体，与末端炔烃的反应区域选择性地产生三取代的苯。
• Supramolecular Catalysis of Unimolecular Rearrangements:  Substrate Scope and Mechanistic Insights
  作者：Dorothea Fiedler、Herman van Halbeek、Robert G. Bergman、Kenneth N. Raymond

  DOI：10.1021/ja062329b

  日期：2006.8.1

  hypothesis is also supported by quantitative NOE studies of two encapsulated substrates, which place the two reacting carbon atoms in close proximity. The capsule can act as a true catalyst, since release and hydrolysis facilitate catalytic turnover. The question of product hydrolysis was addressed through detailed kinetic studies. We conclude that the iminium product must dissociate from the cavity interior

  包含空腔的金属配体组件被用作烯丙基烯铵阳离子的 3-氮杂 Cope 重排的催化宿主。结合后，所有研究的底物的重排速度都会加快，高达 850 倍。为了了解加速的起源，测量了三种烯铵阳离子的活化参数。这些参数表明超分子结构能够降低重排的熵和焓障碍，并且对底物的微小结构变化高度敏感。空间限制性空腔优先结合紧密堆积的、预先组织的底物构象，类似于过渡态的构象。这一假设也得到了两种封装底物的定量 NOE 研究的支持，使两个反应的碳原子靠得很近。胶囊可以充当真正的催化剂，因为释放和水解促进催化转化。通过详细的动力学研究解决了产物水解的问题。我们得出结论，亚胺盐产物必须在氢氧化物介导的水解之前从腔内部和组件外部解离，并提出聚阴离子主体与现有产物的紧密离子对的中介。
• Liquid crystal alkenyl bicyclo[2.2.2]octanes and mixtures and devices containing such compounds
  申请人：The Secretary of State for Defence in Her Britannic Majesty's Government of the United Kingdom of Great Britain and Northern Ireland

  公开号：US06187393B1

  公开（公告）日：2001-02-13

  Compounds of formula (I) are provided which are particularly useful in super twisted nematic devices, where n may be 0-5; m may be 0-5; p may be 1-9; q may be 1, 1, or 2; A1, A2 are independently chosen from 1-4, -disubstituted benzene, 2,5-disubstituted pyrimidine, or 2,5-disubstituted pyridine, trans- 1,4-disubstituted cyclohexane, trans- 2,5-disubstitued dioxane. The aromatic rings may be laterally substituted with F, Cl, Br or CN; Z1 may be O, COO, OOC; Z2, Z3 are independent chosen from a direct bond, COO, OOC, C2H4, CH2O, OCH2, or -c≡c-, provided that when Z1 is O and m is 1, 3 or 5 the carbon—carbon double bond configuration is E; provided that when Z1 is O and m is 2 or 4 the carbon—carbon double bond configuration is Z; provided that when Z1 is COO or OOC and m is 0, 2 or 4 the carbon—carbon double bond configuration is E; and provided that when Z1 is COO or OOC and m is 1, 3 or 5 the carbon—carbon double bond configuration is Z.

  提供了化学式（I）的化合物，特别适用于超扭曲向列型液晶器件，其中n可以为0-5；m可以为0-5；p可以为1-9；q可以为1,1或2；A1，A2独立选择自1-4，-二取代苯，2,5-二取代嘧啶，或2,5-二取代吡啶，反-1,4-二取代环己烷，反-2,5-二取代二噁烷。芳香环可以侧基取代F，Cl，Br或CN；Z1可以为O，COO，OOC；Z2，Z3独立选择自直接键，COO，OOC，C2H4，CH2O，OCH2或-c≡c-，前提是当Z1为O且m为1，3或5时，碳-碳双键构型为E；当Z1为O且m为2或4时，碳-碳双键构型为Z；当Z1为COO或OOC且m为0，2或4时，碳-碳双键构型为E；当Z1为COO或OOC且m为1，3或5时，碳-碳双键构型为Z。
• Palladium-Catalyzed Benzannulation from Alkynes and Allylic Compounds
  作者：Naofumi Tsukada、Shuichi Sugawara、Keiichiro Nakaoka、Yoshio Inoue

  DOI：10.1021/jo026857r

  日期：2003.7.1

  Various alkynes reacted with allyl tosylates in the presence of palladium catalysts, giving polysubstituted benzenes with good to high regioselectivity. Pentasubstituted and trisubstituted benzenes were readily prepared by reaction of internal alkynes and terminal alkynes, respectively. The combination of allyl alcohols and p-toluenesulfonic anhydride could be utilized in place of isolated allyl tosylates. The cyclization of diynes with allyl tosylate afforded bicyclic compounds containing an aromatic ring.
• Supramolecular Catalysis of a Unimolecular Transformation: Aza-Cope Rearrangement within a Self-Assembled Host
  作者：Dorothea Fiedler、Robert G. Bergman、Kenneth N. Raymond

  DOI：10.1002/anie.200461776

  日期：2004.12.10