(R)-ethynyl p-tolyl sulfoxide | 99930-83-3

• 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: (R)-ethynyl p-tolyl sulfoxide
• 英文别名: (-)-(S)-ethynyl p-tolyl sulfoxide；1-[(S)-ethynylsulfinyl]-4-methylbenzene
• CAS: 99930-83-3
• 化学式: C₉H₈OS
• 分子量: 164.228
• InChiKey: UUBXCGJXEGMPMI-NSHDSACASA-N

物化性质

• 熔点：
  38-40 °C
• 沸点：
  70-80 °C(Press: 0.3 Torr)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.11
• 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：

  (R)-ethynyl p-tolyl sulfoxide 在 溶剂黄146 、 sodium iodide 作用下， 反应 1.5h， 以87%的产率得到(R)-(Z)-2-iodo-1-p-tolylsulfinylethene
  参考文献：
  名称：

  Synthesis of Enantiopure 2-Malonylvinyl Sulfoxides via Addition-Elimination Reactions of 2-Halo- and 2-(Mesyloxy)vinyl Sulfoxides

  摘要：

  Enantiomerically pure (E)-2-bromo- and (E)-2-iodovinyl sulfoxides 3a and 3b have been prepared in multigram quantities from (E)-1,2-bis(tri-n-butylstannyl)ethene; enantiomerically pure (E)-2-(mesyloxy) vinyl sulfoxide 3c has been synthesized by reaction of the enolate derived from condensation of 1-lithiomethyl p-tolyl sulfoxide and DMF with methanesulfonyl chloride. These compounds react with anions derived from diethyl alkylmalonates to produce enantiopure 2-malonylvinyl sulfoxides in good to excellent yields and with a high degree of stereoselectivity. The transformations proceed through an ''addition-rotation-elimination'' sequence, and the stereochemical results reinforce the concept that nucleophilic additions to vinyl sulfoxides are sterically controlled and occur predominately syn to the sulfinyl electron lone pair.

  DOI：

  10.1021/jo00090a042

文献信息

• Carbocupration/Zinc Carbenoid Homologation and β-Elimination Reactions for a New Synthesis of Allenes − Application to the Enantioselective Synthesis of Chiral Allenes by Deracemization of sp3-Organometallic Derivatives
  作者：Jos P. Varghese、Irena Zouev、Lionel Aufauvre、Paul Knochel、Ilan Marek

  DOI：10.1002/1099-0690(200212)2002:24<4151::aid-ejoc4151>3.0.co;2-s

  日期：2002.12

  straightforward carbocupration/zinc homologation/β-elimination reaction sequence allows the one-pot synthesis of polysubstituted allenes from acetylenic sulfoxides in excellent isolated chemical yields. Secondary zinc carbenoids were used for the homologation reaction, and so a new synthesis of 1,1-diiodoalkanes is described. This methodology also allows the synthesis of chiral allenes through thermodynamic

  一种新的、直接的碳化/锌同系化/β-消除反应序列允许从炔亚砜以优异的分离化学产率一锅法合成多取代的丙二烯。二级锌卡宾用于同系化反应，因此描述了 1,1-二碘烷烃的新合成。该方法还允许通过二级有机金属衍生物的热力学平衡来合成手性丙二烯。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2002)
• Asymmetric Intramolecular Michael Addition of α-Sulfinyl Vinylic Carbanion to Enoates
  作者：Naoyoshi Maezaki、Hiroaki Sawamoto、Sachiko Yuyama、Ryoko Yoshigami、Tomoko Suzuki、Mayuko Izumi、Hirofumi Ohishi、Tetsuaki Tanaka

  DOI：10.1021/jo0492923

  日期：2004.9.1

  The first example of an asymmetric intramolecular Michael addition reaction with use of α-lithiated vinylic sulfoxide as a Michael donor is reported. Michael addition of the α-lithiated vinylic sulfoxide to (Z)-enoates proceeds with high diastereoselectivity to give the adducts with (R)-configuration at the β-position of the ester in the five-membered-ring formation. The selectivity was reversed in

  报道了使用α-锂化的乙烯基亚砜作为迈克尔供体的不对称分子内迈克尔加成反应的第一个例子。将α-锂化的乙烯基亚砜迈克尔加成到（Z）-烯酸酯上，具有高的非对映选择性，从而在五元环形成中在酯的β-位得到具有（R）-构型的加合物。在六元环形成中，选择性相反。使所得的酯烯醇化物与烷基卤化物或苯甲醛以高非对映选择性反应。
• Synthesis of cis-3-hydroxypipecolic acid via SmI2-mediated cyclization of aldehydo β-aminovinyl sulfoxides
  作者：Hea Seung Chung、Won Kyo Shin、Soo Young Choi、Young Keun Chung、Eun Lee

  DOI：10.1016/j.tetlet.2009.11.116

  日期：2010.1

  Stereoselective synthesis of cis-3-hydroxypipecolic acid was achieved via chirality transfer in the SmI2-mediated cyclization reactions of aldehydo β-aminovinyl sulfoxides.

  通过手性转移在SmI 2介导的醛基β-氨基乙烯基亚砜环化反应中实现了顺式-3-羟基哌酸的立体选择性合成。
• Chiral Sulfur Functional Groups as Definers of the Chirality at the Metal in Ir and Rh Half-Sandwich Complexes: A Combined CD/X-ray Study
  作者：Marta G. Avello、María Frutos、María C. de la Torre、Alma Viso、Marina Velado、Roberto Fernández de la Pradilla、Miguel A. Sierra、Heinz Gornitzka、Catherine Hemmert

  DOI：10.1002/chem.201702662

  日期：2017.10.17

  Mesoionic carbenes (MICs) derived from triazolium salts that contain chiral sulfoxide or sulfoximine functional groups were used to construct enantiopure chiral‐at‐metal IrIII and RhIII half‐sandwich complexes through the synthetic sequence of MIC complexation/C−H aromatic activation. The process was efficient and diastereoselective for the formation of enantiopure five‐membered metallacycles. The

  通过含有MIC络合物/ CH-H芳族活化序列的合成序列，由三唑鎓盐衍生而来的中离子卡宾（MIC）用于手性亚金属Ir III和Rh III半夹心复合物，构成对映体纯的手性金属Ir III和Rh III半三明治复合物。该过程对于形成对映纯五元金属环来说是高效且非对映选择性的。手性硫基对映体的使用使我们能够制备在金属中心具有相反构型的配合物。阳离子的Ir的形成过程中，观察到在金属中心的结构的完全保留III复合物并且在炔烃插入铱III-C键，如圆二色性/ X射线研究所证实。这些结果表明了一种类似S N 1的邻近辅助机制。
• Stereoselective 6-exo Radical Cyclization Using <i>cis</i>-Vinyl Sulfoxide: Practical Total Synthesis of CTX3C
  作者：Shuji Yamashita、Yuuki Ishihara、Hiroyuki Morita、Junichi Uchiyama、Katsutoshi Takeuchi、Masayuki Inoue、Masahiro Hirama

  DOI：10.1021/np100729d

  日期：2011.3.25

  Ciguatoxins, the principal causative toxins of ciguatera seafood poisoning, are large ladder-like polycyclic ethers. We report a highly stereoselective 6-exo radical cyclization/ring-closing olefin metathesis sequence to construct the syn/trans-fused polyether system. The new method was applied to the practical synthesis of ciguatoxin CTX3C.

  Ciguatoxins是Ciguatera海鲜中毒的主要致病性毒素，是大的梯状多环醚。我们报道了高度立体选择性的6-exo自由基环化/闭环烯烃复分解序列，以构建顺式/反式-融合的聚醚系统。该新方法被应用于实际合成雪卡毒素CTX3C。