(S_S,S_S)-1,1-di-p-tolylsulfinyl-3-methyl-but-1-ene | 443640-86-6

• 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_S,S_S)-1,1-di-p-tolylsulfinyl-3-methyl-but-1-ene
• 英文别名: 1-methyl-4-[(S)-[3-methyl-1-[(S)-(4-methylphenyl)sulfinyl]but-1-enyl]sulfinyl]benzene
• CAS: 443640-86-6
• 化学式: C₁₉H₂₂O₂S₂
• 分子量: 346.514
• InChiKey: JTRREVGAMGYWLA-GOTSBHOMSA-N

物化性质

• 沸点：
  591.5±50.0 °C(Predicted)
• 密度：
  1.24±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  72.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S_S,S_S)-1,1-di-p-tolylsulfinyl-3-methyl-but-1-ene 在 正丁基锂 、 乙醇 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.0h， 以55%的产率得到(S(S),S(S))-1,1-bis-p-tolylsulfinyl-3-methylbutane
  参考文献：
  名称：

  Diastereoselective Synthesis of Enantiopure Acyclic β,β′-Disubstituted Vinylsulfoxides

  摘要：

  Thermal elimination of sulfenic acid from enantiopure beta,beta'-disubstituted bis-sulfoxides allows the stereoselective synthesis of enantiopure acyclic beta,beta'-disubstituted vinylsulfoxides. This mild and stereospecific synthesis provides either (E) or (Z) vinylsulfoxides in high yields and is compatible with acid or base sensitive functional groups.

  DOI：

  10.1021/ol800368g
• 作为产物：
  描述：

  (S_S,S_S)-1,1-di-p-tolylsulfinyl-3-methyl-butan-2-ol 在 1-c-hexyl-3-(2-morpholinoethyl)-carbodiimide metho-O-Ts 、 1-环己基-3-[2-(4-吗啉基)乙基]碳化二亚胺 、 copper dichloride 作用下， 以 乙腈 为溶剂， 反应 3.0h， 以90%的产率得到(S_S,S_S)-1,1-di-p-tolylsulfinyl-3-methyl-but-1-ene
  参考文献：
  名称：

  Reactivity of the lithium anion of the (S,S)-bis-p-tolylsulfinyl methane. A versatile synthesis of enantiopure alkylidene 1,1-bis-p-tolylsulfoxides

  摘要：

  We describe herein a new synthesis of enantiopure alkylidene 1,1-bis-p-tolyl-sulfoxides (5), based on a two-steps sequence. The first one involves the alkylation of the lithium anion of the (S,S)-bis-p-tolylsulfinylmethane (1) with aldehydes. The second one consists in a mild dehydration of the sulfinyl alcohols 3 and 4 with the morpho CDI reagent. Some features (reactivity, diastereoselectivity) of the alkylation reaction are discussed. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(01)01210-4

文献信息

• Conjugate Additions to Alkylidene Bis(Sulfoxides)
  作者：Franck Brebion、Guillaume Vincent、Saloua Chelli、Ophélie Kwasnieski、Francisco Najera、Bénédicte Delouvrié、Ilan Marek、Etienne Derat、Jean-Philippe Goddard、Max Malacria、Louis Fensterbank

  DOI：10.1002/asia.201000904

  日期：2011.7.4

  A general study on the conjugate addition of anionic nucleophiles to alkylidene bis(sulfoxides) is presented. Alkoxides gave high yielding and diastereoselective addition reactions, which could be influenced by solvents and the counteranion. Azides provided an interesting entry into sulfinyl‐substituted triazoles. Organometallics, mainly copper reagents, proved also to be valuable nucleophiles, and

  提出了将阴离子亲核试剂共轭加成至亚烷基双（亚砜）的一般研究。醇盐产生高产率和非对映选择性的加成反应，这可能会受到溶剂和抗衡阴离子的影响。叠氮化物为亚磺酰基取代的三唑提供了有趣的入口。有机金属化合物，主要是铜试剂，也被证明是有价值的亲核试剂，并且在与后者的加成反应中完全转化了立体选择性。建模为观察到的非对映选择性提供了理论依据。
• Enolate Conjugate Addition to Alkylidene Bis-Sulfoxides: Sphaeric Acid Synthesis and Absolute Configuration Determination
  作者：Louis Fensterbank、Max Malacria、Franck Brebion、Jean-Philippe Goddard、Catherine Gomez

  DOI：10.1055/s-2006-933122

  日期：——

  The first stereoselective synthesis of sphaeric acid is described. The key step of this synthesis is an efficient ester enolate conjugate addition onto alkylidene bis-sulfoxides with good to high diastereoselectivity. Formation of sphaeric acid allowed the determination of its absolute configuration as 2R.3R.

  描述了球形酸的第一次立体选择性合成。该合成的关键步骤是将有效的酯烯醇化物共轭加成到亚烷基双亚砜上，并具有良好到高的非对映选择性。球形酸的形成允许确定其绝对构型为 2R.3R。
• Oxidation of bis-sulfinyl carbanions as the pivot of ionic/radical tandem reactions
  作者：Guillaume Vincent、Saloua Cheli、Rocio Martinez Mallorquin、Adi Abramovitch、Sophie Beauvière、Catherine Gomez、Franck Brebion、Ilan Marek、Max Malacria、Jean Philippe Goddard、Louis Fensterbank

  DOI：10.1016/j.crci.2015.11.012

  日期：2016.3

  alkylidene bis-sulfoxides proceed with high diastereoselectivity. The oxidation of the resulting carbanions with iron(III) salts induces the radical cyclizations onto alkenes with a high diastereoselectivity leading to enantiopure carbo- or heterocycles. Moreover, allylic radicals have been generated by deprotonation or [1,6]-conjugate addition from alkylidene bis-sulfoxides followed by oxidation.

  摘要 各种亲核试剂如锂化氨基甲酸酯、醇盐或酯烯醇化物的 [1,4]-加成以高非对映选择性进行对映纯亚烷基双亚砜。生成的碳负离子与铁 (III) 盐的氧化诱导自由基环化到烯烃上，具有高非对映选择性，导致对映纯碳或杂环。此外，烯丙基自由基已通过去质子化或 [1,6]-共轭加成从亚烷基双亚砜随后氧化产生。
• Highly diastereoselective ionic/radical domino reactions: single electron transfer induced cyclization of bis-sulfoxides
  作者：Jean-Philippe Goddard、Catherine Gomez、Franck Brebion、Sophie Beauvière、Louis Fensterbank、Max Malacria

  DOI：10.1039/b705284g

  日期：——

  SET oxidation of bis-sulfinyl anions has enabled the uses of bis-sulfinyl radical as a synthetic equivalent of chiral acyl and methylene radicals involved in tandem reactions leading to the enantioselective construction of various carbo- and heterocyclic derivatives.

  双亚磺酰基阴离子的SET氧化使得能够使用双亚磺酰基自由基作为参与串联反应的手性酰基和亚甲基自由基的合成等价物，从而导致各种碳和杂环衍生物的对映选择性结构。
• Convergent Preparation of Enantiomerically Pure Polyalkylated Cyclopropane Derivatives
  作者：Adi Abramovitch、Louis Fensterbank、Max Malacria、Ilan Marek

  DOI：10.1002/anie.200802093

  日期：2008.8.25