toluene-4-sulfonic acid 1-methylpent-4-enyl ester | 171557-94-1

• 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: toluene-4-sulfonic acid 1-methylpent-4-enyl ester
• 英文别名: 4-toluenesulfonic acid 1-methyl-4-pentenyl ester；1-methylpent-4-enyl-tosylate；5-Hexen-2-ol, 2-(4-methylbenzenesulfonate)；hex-5-en-2-yl 4-methylbenzenesulfonate
• CAS: 171557-94-1
• 化学式: C₁₃H₁₈O₃S
• 分子量: 254.35
• InChiKey: YRTJIVHROIJGAW-UHFFFAOYSA-N

物化性质

• 沸点：
  364.1±21.0 °C(Predicted)
• 密度：
  1.097±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 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：

  toluene-4-sulfonic acid 1-methylpent-4-enyl ester 在 2-萘硫醇 作用下， 以 氘代苯 、 N,N-二甲基甲酰胺 为溶剂， 反应 14.08h， 生成 2-甲基四氢吡喃
  参考文献：
  名称：

  Ring Closure Reactions of Substituted 4-Pentenyl-1-oxy Radicals. The Stereoselective Synthesis of Functionalized Disubstituted Tetrahydrofurans

  摘要：

  N-(Alkyloxy)pyridine-2( VT)-thiones 3 and benzenesulfenic acid O-esters 5 have been synthesized from substituted 4-pentenols 1 or the derived tosylates. Compounds 3 and 5 are efficient sources of free alkoxy radicals 6 which undergo synthetically useful fast ring closure reactions 6 --> 8 [k(exo) = (2 +/- 1) x 10(8) s(-1) to (6 +/- 2) x 10(9) s(-1) (T = 30 +/- 0.2 degrees C)]. Tetrahydrofurfuryl radicals 8 can be trapped with, e.g., hydrogen or chlorine atom donors to afford either trans- or cis-disubstituted tetrahydrofurans 10 or 12 depending on the substitution pattern of the 4-pentenyloxy radical. Substituted tetrahydropyrans 11 or 13 are formed in the minor 6-endo-trig cyclization. According to the data of competition kinetics, the observed stereoselectivities in free alkoxy radical cyclizations arise from steric interactions between the substituents in the transition state of the ring closure reactions. Alkyl substituents cause small differences in the measured relative rate constants of B-exo cyclizations which are reminiscent of the data obtained from the rearrangements of alkyl-substituted 5-hexenyl radicals. Likewise, a stereochemical model for oxygen radical cyclization is proposed where the pentenyloxy chain adopts a six-membered, chairlike transition state with the alkyl substituents preferentially situated in the pseudoequatorial positions leading to 2,5-trans-, 2,4-cis-, and 2,3-trans-substituted tetrahydrofurfuryl radicals 8 as the major intermediates.

  DOI：

  10.1021/jo00126a021
• 作为产物：
  描述：

  5-己烯-2-醇 以65%的产率得到
  参考文献：
  名称：

  ASHCROFT, M. R.;BOUGEARD, P.;BURY, A.;COOKSEY, CH. J.;JOHNSON, M. D.;HUNG+, J. ORG. CHEM., 1984, 49, N 10, 1751-1761

  摘要：

  DOI：

文献信息

• Visible‐Light‐Induced <i>ortho</i> ‐Selective Migration on Pyridyl Ring: Trifluoromethylative Pyridylation of Unactivated Alkenes
  作者：Jinwon Jeon、Yu‐Tao He、Sanghoon Shin、Sungwoo Hong

  DOI：10.1002/anie.201912746

  日期：2020.1.2

  alkenes. The overall process is initiated by the selective addition of a CF3 radical to the alkene to provide a nucleophilic alkyl radical intermediate, which enables an intramolecular endo addition exclusively to the ortho-position of the pyridinium salt. Both secondary and tertiary alkyl radicals are well-suited for addition to the C2-position of pyridinium salts to ultimately provide synthetically

  对于未活化的烯烃的位点选择性三氟甲基化吡啶基化，已经实现了在吡啶基环上的光催化邻位选择性迁移。整个过程是通过将CF3自由基选择性地添加到烯烃中以提供亲核烷基自由基中间体而启动的，该中间体能够将分子内的内含物专门添加到吡啶鎓盐的邻位。仲烷基和叔烷基都非常适合于添加吡啶鎓盐的C 2-位，以最终提供具有合成价值的C 2-氟烷基官能化的吡啶。此外，该方法已成功应用于以P为中心的自由基的反应。复杂生物活性分子的后期功能化进一步证明了这种转化的效用。
• Enantiopure 2,9‐Dideuterodecane – Preparation and Proof of Enantiopurity
  作者：Nico Mitschke、Gülsera Eruçar、Miriam H. Fsadni、Amy R. Roberts、Majid M. Sadeghi、Bernard T. Golding、Jens Christoffers、Heinz Wilkes

  DOI：10.1002/ejoc.202100360

  日期：2021.7.22

  Optically active (S,S)-(2,9-2H2)-n-decane was prepared in five steps from (R)-propylene oxide. Its optical purity was determined at the stage of (S)-(5-2H2)-1-hexene, being an intermediate of the synthetic approach, by NMR spectroscopy after Wacker oxidation and enantioselective α-hydroxylation. (R,R)-(2,9-2H2)-n-decane was prepared analogously.

  光学活性的（小号，小号） - （2,9- 2 ħ 2） - ñ -癸烷在由（五个步骤制备- [R ）-氧化丙烯。其光学纯度在 ( S )-(5- 2 H 2 )-1-己烯阶段测定，作为合成方法的中间体，在瓦克氧化和对映选择性α-羟基化后通过核磁共振光谱测定。( R , R )-(2,9- 2 H 2 )-正癸烷类似地制备。
• Determining the Scope of the Organolanthanide-Catalyzed, Sequential Intramolecular Amination/Cyclization Reaction:  Formation of Substituted Quinolizidines, Indolizidines, and Pyrrolizidines
  作者：Gary A. Molander、Shawn K. Pack

  DOI：10.1021/jo035205f

  日期：2003.11.1

  The scope of the lanthanide-mediated, intramolecular amination/cyclization reaction was determined for the formation of substituted quinolizidines, indolizidines, and pyrrolizidines. A methyl group was installed at diverse positions in the substrates to determine the sense and magnitude of diastereoselection. High diastereoselectivity (>20:1) was achieved for the formation of some quinolizidines and

  确定了镧系元素介导的分子内胺化/环化反应的范围，以形成取代的喹oli嗪，吲哚并idine和吡咯并idine。甲基被安装在基板中的不同位置，以确定非立体定向的意义和大小。对于一些喹di嗪和吲哚并idine啶的形成，实现了高非对映选择性（> 20：1）。相对非对称感应的感觉与先前研究的系统相反，尽管仍然存在一些问题，但对这些结果提出了合理化的建议。
• Arene Activation through Iminium Ions: Product Diversity from Intramolecular Photocycloaddition Reactions
  作者：Johanna Proessdorf、Christian Jandl、Thomas Pickl、Thorsten Bach

  DOI：10.1002/anie.202208329

  日期：2022.10.4

  Benzaldehyde-derived iminium ions 1 form benzoxacyclic products 2 in a photochemical reaction cascade (n=0,1). Structurally different products 3 (meta photocycloaddition) and 4 (aza Paternò–Büchi reaction) are observed depending on two key substituents (R, R1).

  苯甲醛衍生的亚胺离子1在光化学级联反应中形成苯并氧杂环产物2 ( n= 0,1)。根据两个关键取代基（R、R 1 ）观察到结构不同的产物3 （间位光环加成）和4 （aza Paternò-Büchi 反应）。
• Ring Closure Reactions of Substituted 4-Pentenyl-1-oxy Radicals. The Stereoselective Synthesis of Functionalized Disubstituted Tetrahydrofurans
  作者：Jens Hartung、Fabienne Gallou

  DOI：10.1021/jo00126a021

  日期：1995.10

  N-(Alkyloxy)pyridine-2( VT)-thiones 3 and benzenesulfenic acid O-esters 5 have been synthesized from substituted 4-pentenols 1 or the derived tosylates. Compounds 3 and 5 are efficient sources of free alkoxy radicals 6 which undergo synthetically useful fast ring closure reactions 6 --> 8 [k(exo) = (2 +/- 1) x 10(8) s(-1) to (6 +/- 2) x 10(9) s(-1) (T = 30 +/- 0.2 degrees C)]. Tetrahydrofurfuryl radicals 8 can be trapped with, e.g., hydrogen or chlorine atom donors to afford either trans- or cis-disubstituted tetrahydrofurans 10 or 12 depending on the substitution pattern of the 4-pentenyloxy radical. Substituted tetrahydropyrans 11 or 13 are formed in the minor 6-endo-trig cyclization. According to the data of competition kinetics, the observed stereoselectivities in free alkoxy radical cyclizations arise from steric interactions between the substituents in the transition state of the ring closure reactions. Alkyl substituents cause small differences in the measured relative rate constants of B-exo cyclizations which are reminiscent of the data obtained from the rearrangements of alkyl-substituted 5-hexenyl radicals. Likewise, a stereochemical model for oxygen radical cyclization is proposed where the pentenyloxy chain adopts a six-membered, chairlike transition state with the alkyl substituents preferentially situated in the pseudoequatorial positions leading to 2,5-trans-, 2,4-cis-, and 2,3-trans-substituted tetrahydrofurfuryl radicals 8 as the major intermediates.