3-ethenyl-1-butanol tosylate | 86646-40-4

• 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: 3-ethenyl-1-butanol tosylate
• 英文别名: toluene-p-sulphonate of 3-methylpent-4-en-1-ol；toluene-4-sulfonic acid 3-methylpent-4-enyl ester；3-Methylpent-4-enyl 4-methylbenzenesulfonate
• CAS: 86646-40-4
• 化学式: C₁₃H₁₈O₃S
• 分子量: 254.35
• InChiKey: GSNOHKUJLANJIX-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)：
  3.2
• 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：

  3-ethenyl-1-butanol tosylate 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 四氢-4-甲基-2H-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：

  3-甲基-4-戊烯酸 在 lithium aluminium tetrahydride 作用下， 以 吡啶 、 乙醚 为溶剂， 生成 3-ethenyl-1-butanol tosylate
  参考文献：
  名称：

  Understanding the effect of allylic methyls in olefin cross-metathesis

  摘要：

  A series of NMR spectroscopy experiments have been conducted with both the model compound, 3-methyl-1-pentene and the corresponding ADMET monomer 3,6,9-trimethylundeca-1,10-diene (11) to better understand the effect of allylic methyls during olefin metathesis chemistry. Traditional ADMET catalysts such as Schrock's molybdenum (1), and Grubbs' ruthenium 1st and 2nd generation (2 and 3) were examined under cross-metathesis and ADMET conditions. Regardless of catalyst selection, 50% or less metathesis conversion was observed for all reactions, especially in the case of the more sterically encumbered diene. With Schrock's molybdenum catalyst 1, the reaction leads to an accumulation of the non-productive metallacyclobutane, trapping the catalyst in an inactive form. With Grubbs' ruthenium catalysts 2 and 3, the substrate coordinates to the metal center primarily to yield non-productive metathesis, which results in a build-up of the methylidene complex leading to catalyst decomposition. These results are directly correlated to the orientation of the substrate's bulk during the metallacyclobutane formation, the alkyl branch being adjacent to the metal center in the case of the molybdenum catalyst 1, and opposite to it in the case of ruthenium catalyst 2 and 3. (c) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2005.09.030

文献信息

• 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。
• Beckwith, Athelstan L. J.; Moad, Graeme, Journal of the Chemical Society. Perkin transactions II, 1980, p. 1083 - 1092
  作者：Beckwith, Athelstan L. J.、Moad, Graeme

  DOI：——

  日期：——
• Coupling reactions of higher order cuprates with primary halides: extremely mild and efficient substitution reactions of bromides and chlorides
  作者：Bruce H. Lipshutz、David Parker、Joseph A. Kozlowski、Robert D. Miller

  DOI：10.1021/jo00167a037

  日期：1983.9
• LIPSHUTZ, B. H.;PARKER, D.;KOZLOWSKI, J. A.;MILLER, R. D., J. ORG. CHEM., 1983, 48, N 19, 3334-3336
  作者：LIPSHUTZ, B. H.、PARKER, D.、KOZLOWSKI, J. A.、MILLER, R. D.

  DOI：——

  日期：——
• 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.