(E)-hex-4-en-1-yl 4-methylbenzenesulfonate | 25143-95-7

• 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: (E)-hex-4-en-1-yl 4-methylbenzenesulfonate
• 英文别名: (4E)-4-hexenyl 4-methylbenzenesulfonate；[(E)-hex-4-enyl] 4-methylbenzenesulfonate
• CAS: 25143-95-7
• 化学式: C₁₃H₁₈O₃S
• 分子量: 254.35
• InChiKey: JUODBZUNPMIVHO-ONEGZZNKSA-N

物化性质

• 沸点：
  373.0±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)：
  3.1
• 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：

  (E)-hex-4-en-1-yl 4-methylbenzenesulfonate 在 sodium iodide 作用下， 以 丙酮 为溶剂， 以85%的产率得到trans-2-hexenyl iodide
  参考文献：
  名称：

  Regiochemical and stereochemical studies on halocyclization reactions of unsaturated sulfides

  摘要：

  The regiochemistry and stereochemistry for the halocyclization reactions of unsaturated benzyl sulfides have been examined as a function of tether length, type of unsaturation (carbon-carbon double bond versus carbon-carbon triple bond), substituents, and halogenating agent. Alkenyl sulfides were found to react with iodine or bromine at room temperature to give five-membered ring cycloadducts exclusively over those having four-membered rings, while for larger systems, six-membered ring products are formed preferentially over their five-membered ring isomers and exclusively over the seven-membered ring adducts. The endo- versus exo-regioselectivity of these alkenyl sulfide ring closures most likely reflects the difference in thermodynamic stabilities of the beta-halo sulfide cycloadducts, which are able to equilibrate via a common episulfonium intermediate. The efficiency of the cyclization process markedly drops off for these alkenyl sulfides as the tether length increases beyond four intervening carbon centers. Thus, while the halogenations of 3-butenyl sulfides and 4-pentenyl sulfides give high yields of cycloadducts, those of 5-hexenyl sulfides afford only small amounts of cyclized products and large quantities of acyclic dibromides. Conversely the reactions of acetylenic sulfides with iodine give uniformly high yields and regiochemical control regardless of the tether length. Thus, 3-butynyl and 4-pentynyl sulfides cyclize cleanly to the five-membered ring while 5-hexynyl sulfides give exclusively the six-membered ring, The products arising from these alkynyl sulfide ring closures are believed to be formed under kinetic control. The methodology has been applied to the synthesis of unusual bicyclic beta-lactams related to the penicillin family of antibiotics.

  DOI：

  10.1021/jo00125a038
• 作为产物：
  描述：

  Ethyl 4-hexenoate 在 吡啶 、 lithium aluminium tetrahydride 作用下， 以 二氯甲烷 为溶剂， 生成 (E)-hex-4-en-1-yl 4-methylbenzenesulfonate
  参考文献：
  名称：

  Iodide-Catalysed Cyclization of Unsaturated N-Chloroamines: A New Way to Synthesise 3-Chloropiperidines

  摘要：

  DOI：

  10.1002/1099-0690(200209)2002:18<3171::aid-ejoc3171>3.0.co;2-l

文献信息

• Regioselective Epoxidations by Cytochrome P450 3A4 Using a Theobromine Chemical Auxiliary to Predictably Produce N-Protected β- or γ-Amino Epoxides
  作者：Vanja Polic、Kin Jack Cheong、Fabien Hammerer、Karine Auclair

  DOI：10.1002/adsc.201700637

  日期：2017.11.23

  N-Protected β- and γ-amino epoxides are useful chiral synthons. We report here that the enzyme cytochrome P450 3A4 can catalyze the formation of such compounds in a regio- and stereoselective manner, even in the presence of multiple double bonds or aromatic substituents. To this end, the theobromine chemical auxiliary is used not only to control the selectivity of the enzyme, but also as a masked amine

  N-保护的β-和γ-氨基环氧化物是有用的手性合成子。我们在此报告，即使存在多个双键或芳族取代基，细胞色素P450 3A4酶也可以区域和立体选择性方式催化此类化合物的形成。为此，可可碱化学助剂不仅用于控制酶的选择性，而且还用作掩蔽的胺，并促进产物的回收。可可碱可预测地将可可碱基团中第四个碳的双键定向环氧化。与大多数催化剂不同，选择性不取决于电子或空间因素，而是取决于烯烃相对于可可碱的位置。
• Photochemical Reaction Cascade from <i>O</i>-Pent-4-enyl-Substituted Salicylates to Complex Multifunctional Scaffolds
  作者：Andreas Zech、Thorsten Bach

  DOI：10.1021/acs.joc.8b00238

  日期：2018.3.16

  The arene ring of the title compounds is cleaved by a reaction cascade which is initiated by an intramolecular ortho photocycloaddition reaction. Tricyclic products were obtained in a highly regio- and diastereoselective fashion via a cyclooctatriene intermediate. The facial diastereoselectivity exerted by a stereogenic center in the tether is moderate to good (dr = 65/35 to 82/18). Yields were acceptable

  标题化合物的芳烃环被分子内邻位光环加成反应引发的反应级联裂解。通过环辛三烯中间体以高度区域选择性和非对映选择性的方式获得三环产物。系链中立体定位中心施加的面部非对映选择性中等至良好（dr = 65/35至82/18）。产量是可以接受的（44-87％），除了单一基质在系链中具有双甲基双取代作用，并且相应产物的产率仅为14％之外。该反应在烯烃构型（E或Z）方面是立体收敛的，与邻位光环加成步骤的三线态机理相一致。
• A Systematic Study of Unsaturation in Lipid Nanoparticles Leads to Improved mRNA Transfection In Vivo
  作者：Sang M. Lee、Qiang Cheng、Xueliang Yu、Shuai Liu、Lindsay T. Johnson、Daniel J. Siegwart

  DOI：10.1002/anie.202013927

  日期：2021.3.8

  ionizable lipid series (4A3) emerged from in vitro and in vivo screening, where the 4A3 core with a citronellol‐based (Cit) periphery emerged as best. We studied the interaction between LNPs and a model endosomal membrane where 4A3‐Cit demonstrated superior lipid fusion over saturated lipids, suggesting its unsaturated tail promotes endosomal escape. Furthermore, 4A3‐Cit significantly improved mRNA delivery

  脂质纳米粒子 (LNP) 代表了 mRNA 递送的领先概念。不饱和脂质在自然界中发挥着重要作用，具有 mRNA 治疗的潜力，但很难通过化学合成获得。为了系统地研究不饱和度的作用，利用模块化反应来访问由不饱和硫醇合成实现的 91 种氨基脂质库。经过体外和体内筛选，出现了可电离脂质系列 (4A3)，其中具有香茅醇基 (Cit) 外周的 4A3 核心表现最佳。我们研究了 LNP 和模型内体膜之间的相互作用，其中 4A3-Cit 表现出优于饱和脂质的脂质融合，表明其不饱和尾部促进内体逃逸。此外，4A3-Cit 通过选择性器官靶向 (SORT) 显着提高了体内 mRNA 递送效率，导致蛋白表达比亲本 LNP 增加了 18 倍。这些发现深入了解脂质不饱和如何促进 mRNA 递送，并证明脂质混合如何增强功效。
• Complex Carbocyclic Skeletons from Aryl Ketones through a Three‐Photon Cascade Reaction
  作者：Line Næsborg、Christian Jandl、Andreas Zech、Thorsten Bach

  DOI：10.1002/anie.201915731

  日期：2020.3.27

  Starting from readily available 7-substituted 1-indanones, products with a tetracyclo[5.3.1.01,7 04,11 ]undec-2-ene skeleton were obtained upon irradiation at λ=350 nm (eight examples, 49-67 % yield). The assembly of the structurally complex carbon framework proceeds in a three-photon process comprising an ortho photocycloaddition, a disrotatory [4π] photocyclization, and a di-π-methane rearrangement

  从容易获得的7-取代的1-茚满酮开始，在λ= 350 nm照射后获得具有四环[5.3.1.01,7 04,11]十一碳-2-烯骨架的产物（8个实例，产率49-67％） 。结构复杂的碳骨架的组装以三光子过程进行，该过程包括邻位光环加成，可旋转的[4π]光环化和二π-甲烷重排。起始原料的扁平芳烃核通过三个方向的出口向量转化为官能化的多环烃。探索了在中央环丙烷环上的开环反应，其使得能够制备三环[5.3.1.04,11]十一碳烯和三环[6.2.1.01,5]十一碳烯。
• Organolanthanide-Catalyzed Intramolecular Hydroamination/Cyclization/Bicyclization of Sterically Encumbered Substrates. Scope, Selectivity, and Catalyst Thermal Stability for Amine-Tethered Unactivated 1,2-Disubstituted Alkenes
  作者：Jae-Sang Ryu、Tobin J. Marks、Frank E. McDonald

  DOI：10.1021/jo035417c

  日期：2004.2.1

  R* = (−)-menthyl; Ln = Sm, Y), and [Me2Si(η5-Me4C5)(CpR*)]SmN(TMS)2 (Cp = η5-H3C5; R* = (−)-menthyl) mediate asymmetric intramolecular hydroamination/cyclization of amines bearing internal olefins and afford chiral 2-substituted piperidine and pyrrolidine in enantioselectivities as high as 84:16 er at 60 °C. The substrate of the structure NH2CH2CMe2CH2CHCH(CH2)2CHCH2 is regiospecifically bicyclized

  本文报道金属有机催化的分子内加氢胺化/胺-拴系的未活化的1,2-二取代的烯烃，得到使用的类型的配位不饱和复合物相应的单-和二取代的吡咯烷和哌啶环化（η 5 -Me 5 Ç 5）2 LnCH（TMS）2（Ln为La，Sm或），[我2的Si（η 5 -Me 4 ç 5）2 ] SmCH（TMS）2，和[我2的Si（η 5 -Me 4 ç 5）（吨BuN）] LnE（TMS）2（Ln = Sm，Y，Yb，Lu; E = N，CH）作为预催化剂。[我2的Si（η 5 -Me 4 Ç 5）（吨BUN）] LNE（TMS）2所介导的分子内加氢胺化/的空间要求的氨基烯烃，得到在高非对映选择性取代的吡咯烷环化（反式/顺式= 16/1）且产量高到极好。另外，手性Ç 1个的类型[我的-对称金属有机催化剂2的Si（OHF）（CPR *）] LNN（TMS）2（OHF =η 5 -octahydrofluorenyl;