(S)-1-bromo-3-methyl-2-p-tolylsulfinyl-2-butene | 152836-35-6

• 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: (S)-1-bromo-3-methyl-2-p-tolylsulfinyl-2-butene
• 英文别名: 1-[(S)-(1-bromo-3-methylbut-2-en-2-yl)sulfinyl]-4-methylbenzene
• CAS: 152836-35-6
• 化学式: C₁₂H₁₅BrOS
• 分子量: 287.221
• InChiKey: LZZWKSKHQTZOCU-HNNXBMFYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  36.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-1-bromo-3-methyl-2-p-tolylsulfinyl-2-butene 在 lithium aluminium tetrahydride 、 三乙基硼 、 氧气 、 三正丁基氢锡 、 sodium hydride 作用下， 以 四氢呋喃 、 乙醚 、 甲苯 为溶剂， 生成 [(S)-1-Hydroxymethyl-3-isopropylidene-4-(1-methoxy-1-methyl-ethyl)-cyclopentyl]-methanol
  参考文献：
  名称：

  Asymmetric Intramolecular Radical Vinylation Using Enantiopure Sulfoxides as Temporary Chiral Auxiliaries

  摘要：

  A very diastereoselective addition-elimination sequence affords cyclopentane derivatives in high enantiomeric purities. The enantiopure sulfoxide unit serves as a very efficient temporary chiral auxiliary in this tandem reaction. Interestingly, the presence of the MAD Lewis acid totally reverses the stereochemical outcome of this reaction. Several determining parameters of this sequence have been investigated: the substitution of the vinyl sulfoxide moiety, the nature of the prochiral radical, the aromatic substituent of the sulfoxide group, the tether, and the role played by different Lewis acids.

  DOI：

  10.1021/ja992818u
• 作为产物：
  描述：

  (+)-(S)-2-methyl-3-(p-tolylsulfinyl)-3-buten-2-ol 在 N-溴代丁二酰亚胺(NBS) 、 二甲基硫 作用下， 以 二氯甲烷 为溶剂， 反应 17.0h， 以80%的产率得到(S)-1-bromo-3-methyl-2-p-tolylsulfinyl-2-butene
  参考文献：
  名称：

  An easy synthesis of chiral sulfinyl allylic bromides and their use in the preparation of(R)S- and (S)S-2-p-tolylsulfinyl-1,3-alkadienes

  摘要：

  Condensation of (R)-vinyl-p-tolylsulfoxide anion on carbonyl compounds led directly to chiral allylic sulfinylalcohols 1. By treatment with NBS/Me2S, these alcohols 1 were converted into the rearranged primary allylic bromides 2 via SN2' displacement. Optically pure (R)- and (S)-2-p-tolylsulfinyl-1,3-alkadienes 3 resulted from the action of KOH/ROH upon these bromides 2 via E2' eliminations.

  DOI：

  10.1016/s0957-4166(00)80374-2

文献信息

• Titanocene-Mediated Intramolecular Radical Vinylations
  作者：Louis Fensterbank、Emmanuel Lacôte、Max Malacria、Dominique Leca、Kai Song、Matthias Albert、Monica Grangeio Gonçalves

  DOI：10.1055/s-2005-865357

  日期：——

  A new titanium-mediated domino intramolecular radical vinylation is described. It relies on the radical β-elimination of sulfoximyl and phosphinoyl radicals, and leads efficiently to exo-alkylidene pyrrolidines with one stereogenic center β to the nitrogen. The reaction of phosphine oxides has been shown to effectively follow a radical pathway.

  描述了一种新的钛介导的多米诺分子内自由基乙烯基化。它依赖于亚砜基和膦酰基自由基的β-消除，并有效地产生具有一个立体中心β到氮的外-亚烷基吡咯烷。已显示氧化膦的反应有效地遵循自由基途径。
• Iodine(III)-Mediated Preparations of Nitrogen-Containing Sulfur Derivatives: Dramatic Influence of the Sulfur Oxidation State
  作者：Dominique Leca、Kai Song、Muriel Amatore、Louis Fensterbank、Emmanuel Lacôte、Max Malacria

  DOI：10.1002/chem.200305525

  日期：2004.2.20

  Reaction of sulfonamides with iodosobenzene leads to phenyliodinanes. A new catalysis reaction of the decomposition of these products in the presence of sulfoxides that allows the smooth synthesis of sulfoximines has been evidenced and studied: copper(II) salts were used to prepare compounds 4 a-j and 5 b, d, f, j, k from the corresponding, easily prepared, sulfoxides. The reactions proceed with retention

  磺酰胺与碘代苯的反应生成苯基碘烷。已经证明并研究了在亚砜存在下这些产物分解的新催化反应，该反应可以平稳合成亚砜肟类：使用铜（II）盐制备化合物4 aj和5 b，d，f，j，由相应的易于制备的亚砜得到k。反应在硫中心保留构型进行，并且三氟甲磺酸铜（II）是用于亚胺化催化剂的最佳候选者。在制备起始碘丁烷中从磺酰胺转换为亚磺酰胺完全改变了反应途径：不再可获得碘，而是获得了亚磺酰胺7 aj。可以通过从硫中心除去一个氧原子而增加pK（a）来使这种行为合理化。磺酰亚胺盐是具有各种应用的有趣分子。通过在乙腈中进行反应，已经实现了其一锅法合成的优化。立体化学研究表明，尽管对映体纯度受到侵蚀，但转化过程仍在构型整体保留在硫中心的情况下进行。提出了一个解释这一结果的模型。另外，已经解释了氧化的磺酰胺副产物的存在，并且当醇被水代替时，后一种途径成为唯一的途径。获得了良好的氧化产物收率。通过在乙腈中进行反应，已经
• Radical Cyclization/β-Elimination Tandem Reactions: Enantiopure Sulfoxides as Temporary Chiral Auxiliaries
  作者：Emmanuel Lacôte、Bénédicte Delouvrié、Louis Fensterbank、Max Malacria

  DOI：10.1002/(sici)1521-3773(19980817)37:15<2116::aid-anie2116>3.0.co;2-l

  日期：1998.8.17

  Alkylidene-substituted cyclopentane derivatives are formed in high enantiomeric purity by the reaction shown below. A highly diastereoselective radical cyclization is followed by elimination of a β-sulfinyl radical. Interestingly, the addition of the Lewis acid methylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide) (MAD) totally reverses the stereochemical outcome of the reaction. E=CO2 Me.
• An easy synthesis of chiral sulfinyl allylic bromides and their use in the preparation of(R)S- and (S)S-2-p-tolylsulfinyl-1,3-alkadienes
  作者：Eric Bonfand、Pascal Gosselin、Christian Maignan

  DOI：10.1016/s0957-4166(00)80374-2

  日期：1993.7

  Condensation of (R)-vinyl-p-tolylsulfoxide anion on carbonyl compounds led directly to chiral allylic sulfinylalcohols 1. By treatment with NBS/Me2S, these alcohols 1 were converted into the rearranged primary allylic bromides 2 via SN2' displacement. Optically pure (R)- and (S)-2-p-tolylsulfinyl-1,3-alkadienes 3 resulted from the action of KOH/ROH upon these bromides 2 via E2' eliminations.
• Asymmetric Intramolecular Radical Vinylation Using Enantiopure Sulfoxides as Temporary Chiral Auxiliaries
  作者：Bénédicte Delouvrié,、Louis Fensterbank、Emmanuel Lacôte、Max Malacria

  DOI：10.1021/ja992818u

  日期：1999.12.1

  A very diastereoselective addition-elimination sequence affords cyclopentane derivatives in high enantiomeric purities. The enantiopure sulfoxide unit serves as a very efficient temporary chiral auxiliary in this tandem reaction. Interestingly, the presence of the MAD Lewis acid totally reverses the stereochemical outcome of this reaction. Several determining parameters of this sequence have been investigated: the substitution of the vinyl sulfoxide moiety, the nature of the prochiral radical, the aromatic substituent of the sulfoxide group, the tether, and the role played by different Lewis acids.