2-(Benzenesulfonyl)-5-phenyl-1-penten-3-ol | 133834-59-0

• 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: 2-(Benzenesulfonyl)-5-phenyl-1-penten-3-ol
• 英文别名: 2-(Benzenesulfonyl)-5-phenylpent-1-en-3-ol
• CAS: 133834-59-0
• 化学式: C₁₇H₁₈O₃S
• 分子量: 302.394
• InChiKey: YNCMTQFKCUVILA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  62.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(Benzenesulfonyl)-5-phenyl-1-penten-3-ol 在 jones reagent 作用下， 以 丙酮 为溶剂， 以56%的产率得到2-(Benzenesulfonyl)-5-phenyl-1-penten-3-one
  参考文献：
  名称：

  Synthesis and reactions of .alpha.-methylene-.beta.-keto sulfones

  摘要：

  Modified Jones oxidation of 2-(benzenesulfonyl)-2-alken-1-ols and rapid nonnucleophilic workup below 0-degrees-C yields a variety of alpha-methylene-beta-keto sulfones 4, including crystalline parent 4a and also e-h, which can be stored at -20-degrees-C without change. In the absence of nucleophiles, the new compounds are stable (heating in benzene) toward dimerization and polymerization. Thus, selective cross-reactions are feasible. With alcohols, including sterically hindered tertiary alcohols and also with 2-(ethoxycarbonyl)cyclopentanone, the compounds function as efficient Micheal acceptors, even in the absence of base catalysis. In moist ether, 2-(benzenesulfonyl)-1-penten-3-one (4b) suffers rearrangement to 2-(benzenesulfonyl)ethyl propanoate (9). Sulfonylated alcohol 7 and strained alpha-hydroxyoxetane 8 are assumed as intermediates. Toward electron-rich aromatics and heteroaromatics, alpha-methylene-beta-keto sulfones 4 behave as electrophiles in Friedel-Crafts-type functionalizations. The new compounds are also dienophilic: of the two groups (acetyl and benzenesulfonyl) attached to the ethylenic terminus in 4a, benzenesulfonyl has been found to preferentially adopt the endo position in cycloadditions of cyclopentadiene and also cyclohexadiene. Prototype 3-(benzenesulfonyl)-3-buten-2-one (4a) is a crystalline methyl vinyl ketone (MVK) equivalent which, unlike MVK, undergoes controlled free-radical additions with nucleophilic radicals. In hetero-Diels-Alder reactions, 4a serves as a 1-oxa-1,3-butadiene unit, combining with a wide range of alkenes of graded nucleophilicity. Electron deficient 4a also reacts as an enophile toward 1,1-dialkylated ethylenes. In the presence of ZnCl2.OEt2, the ene reaction with beta-piene can be suppressed completely in favor of cycloaddition, giving a robustadial building block in 85% yield. In further applications to natural products chemistry, the synthesis of frontalin and novel oxatricyclics are described.

  DOI：

  10.1021/jo00013a007
• 作为产物：
  描述：

  苯丙醛 、 苯基乙烯基砜 在 三乙烯二胺 作用下， 反应 504.0h， 以46%的产率得到2-(Benzenesulfonyl)-5-phenyl-1-penten-3-ol
  参考文献：
  名称：

  Synthesis and reactions of .alpha.-methylene-.beta.-keto sulfones

  摘要：

  Modified Jones oxidation of 2-(benzenesulfonyl)-2-alken-1-ols and rapid nonnucleophilic workup below 0-degrees-C yields a variety of alpha-methylene-beta-keto sulfones 4, including crystalline parent 4a and also e-h, which can be stored at -20-degrees-C without change. In the absence of nucleophiles, the new compounds are stable (heating in benzene) toward dimerization and polymerization. Thus, selective cross-reactions are feasible. With alcohols, including sterically hindered tertiary alcohols and also with 2-(ethoxycarbonyl)cyclopentanone, the compounds function as efficient Micheal acceptors, even in the absence of base catalysis. In moist ether, 2-(benzenesulfonyl)-1-penten-3-one (4b) suffers rearrangement to 2-(benzenesulfonyl)ethyl propanoate (9). Sulfonylated alcohol 7 and strained alpha-hydroxyoxetane 8 are assumed as intermediates. Toward electron-rich aromatics and heteroaromatics, alpha-methylene-beta-keto sulfones 4 behave as electrophiles in Friedel-Crafts-type functionalizations. The new compounds are also dienophilic: of the two groups (acetyl and benzenesulfonyl) attached to the ethylenic terminus in 4a, benzenesulfonyl has been found to preferentially adopt the endo position in cycloadditions of cyclopentadiene and also cyclohexadiene. Prototype 3-(benzenesulfonyl)-3-buten-2-one (4a) is a crystalline methyl vinyl ketone (MVK) equivalent which, unlike MVK, undergoes controlled free-radical additions with nucleophilic radicals. In hetero-Diels-Alder reactions, 4a serves as a 1-oxa-1,3-butadiene unit, combining with a wide range of alkenes of graded nucleophilicity. Electron deficient 4a also reacts as an enophile toward 1,1-dialkylated ethylenes. In the presence of ZnCl2.OEt2, the ene reaction with beta-piene can be suppressed completely in favor of cycloaddition, giving a robustadial building block in 85% yield. In further applications to natural products chemistry, the synthesis of frontalin and novel oxatricyclics are described.

  DOI：

  10.1021/jo00013a007

文献信息

• Rhodium‐Catalyzed Asymmetric Synthesis of 1,2‐Disubstituted Allylic Fluorides
  作者：Fuad O. Usman、Achyut R. Gogoi、Jason C. Mixdorf、Osvaldo Gutierrez、Hien M. Nguyen

  DOI：10.1002/anie.202314843

  日期：2023.11.27

  Access to enantioenriched 1,2-disubstituted allylic fluorides in good to high levels of enantiomeric excess was achieved using a chiral diene-ligated rhodium catalyst. Experimental results together with DFT calculations support a dynamic kinetic asymmetric transformation process, whose efficiency is impacted by developing steric interactions in the syn and anti π-allyl intermediate complexes.

  使用手性二烯连接的铑催化剂，可以获得对映体过量的对映体富集 1,2-二取代烯丙基氟化物。实验结果以及 DFT 计算支持动态动力学不对称转变过程，其效率受 syn 和抗 π-烯丙基中间体复合物中产生的空间相互作用的影响。
• Dimerization of (e)-2-benzenesulfonyl-1,3-alkadienes the benzenesulfonyl group exerts acyclic stereocontrol
  作者：H.Martin R. Hoffmann、Andreas Weichert、Alexandra M.Z. Slawin、D.J. Williams

  DOI：10.1016/s0040-4020(01)87758-9

  日期：1990.1