(S)-3,3-dimethyl-1-butynyl p-tolyl sulfoxide | 205251-14-5

• 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)-3,3-dimethyl-1-butynyl p-tolyl sulfoxide
• 英文别名: 1-[(S)-3,3-dimethylbut-1-ynylsulfinyl]-4-methylbenzene
• CAS: 205251-14-5
• 化学式: C₁₃H₁₆OS
• 分子量: 220.335
• InChiKey: ILFAZGBFOKVFKX-OAHLLOKOSA-N

物化性质

• 熔点：
  71-72 °C
• 沸点：
  342.7±35.0 °C(Predicted)
• 密度：
  1.10±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 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)-3,3-dimethyl-1-butynyl p-tolyl sulfoxide 以 乙醚 、 甲苯 为溶剂， 反应 0.08h， 生成 (3S,4S,5S)-3-tert-butyl-5-methyl-4-[(R)-p-tolylsulfinyl]-4,5-dihydro-3H-pyrazole-3-carbonitrile
  参考文献：
  名称：

  （Z）-3-对甲苯基亚磺酰基丙烯腈为手性偶极亲和剂：与重氮烷烃的反应。

  摘要：

  [反应：见正文]已用重氮烷评估了对映纯（Z）-3-对甲苯基亚磺酰基丙烯腈（1）的偶极亲和性。当R = H时获得3-氰基吡唑，但当R =烷基（Bn，n-Bu和t-Bu）时，在温和条件下仅以高收率形成一个环加合物（4或5），因此证明了对苯并吡咯的完全控制。区域选择性以及内/外和面部选择性。这些反应是吡唑啉及其相关结构合成的新的直接途径，并揭示了（Z）-亚磺酰基丙烯腈的优异的双亲性特征。

  DOI：

  10.1021/ol016481o
• 作为产物：
  描述：

  (3,3-dimethylbut-1-yn-1-yl)magnesium bromide 、 (-)-menthyl p-toluenesulfinate 以 甲苯 为溶剂， 反应 3.5h， 以81%的产率得到(S)-3,3-dimethyl-1-butynyl p-tolyl sulfoxide
  参考文献：
  名称：

  Synthesis and Dienophilic Behavior of Enantiomerically Pure (Z)-3-p-Tolylsulfinylacrylonitriles

  摘要：

  The syntheses of enantiomerically pure (Z)-3-p-tolylsulfinylacrylonitrile (1b) and its 2-n-butyl (1a), 2-tert-butyl (1c), and 2-benzyl(ld) derivatives, by stereoselective hydrocyanation with Et2AlCN of their corresponding alkynylsulfoxides, are described. Asymmetric Diels-Alder reactions of these dienophiles with cyclopentadiene are also reported, the most significant finding being their total pi-facial diastereoselectivity, controlled by the sulfur configuration, which can be readily invented by using BF3 as a catalyst. The endo selectivity is very high for Ib under thermal and catalytic (ZnBr2) conditions and complete in the presence of BE3 whereas la and Id only exhibit a complete endo selectivity in the presence of BF3.

  DOI：

  10.1021/jo9721002

文献信息

• Highly Stereoselective Synthesis of Functionalized β,β-Di- and Trisubstituted Vinylic Sulfoxides by Cu-Catalyzed Conjugate Addition of Organozinc Reagents
  作者：Naoyoshi Maezaki、Hiroaki Sawamoto、Tomoko Suzuki、Ryoko Yoshigami、Tetsuaki Tanaka

  DOI：10.1021/jo048747l

  日期：2004.11.1

  β,β-Disubstituted chiral vinylic sulfoxides bearing functionalities have been synthesized via Cu-catalyzed conjugate addition of organozinc reagents to chiral 1-alkynyl sulfoxides. Due to the availability of functionalized organozinc reagents and high syn-selectivity of the reaction, both geometric β,β-disubstituted vinylic sulfoxides were selectively synthesized. Furthermore, 1-alkynyl sulfoxides

  通过将有机锌试剂的铜催化共轭加成到手性1-炔基亚砜上，合成了带有官能团的β，β-二取代的手性乙烯基亚砜。由于官能化的有机锌试剂的可获得性和反应的高顺选择性，因此选择性地合成了两种几何的β，β-二取代的乙烯基亚砜。此外，通过用亲电子试剂捕获所得的α-亚磺酰基乙烯基碳负离子，将1-炔基亚砜衍生为三取代的乙烯基亚砜。高度非对映选择性的THF和THP环形成是通过这种方法完成的，然后进行了分子内迈克尔加成。
• Geometrically Selective Synthesis of Functionalized β,β-Disubstituted Vinylic Sulfoxides by Cu-Catalyzed Conjugate Addition of Organozinc Reagents to 1-Alkynyl Sulfoxides
  作者：Naoyoshi Maezaki、Hiroaki Sawamoto、Ryoko Yoshigami、Tomoko Suzuki、Tetsuaki Tanaka

  DOI：10.1021/ol034289b

  日期：2003.4.1

  functionalities has been developed by employing Cu-catalyzed conjugate addition of an organozinc reagent to chiral 1-alkynyl sulfoxide. Since the reaction proceeds with very high syn-selectivity, both geometric beta,beta-disubstituted vinylic sulfoxides were stereoselectively synthesized by changing the combination of 1-alkynyl sulfoxide and the organozinc reagent.

  [反应：见正文]通过将有机锌试剂的铜催化共轭加成到手性1-炔基亚砜上，已开发出一种具有各种功能的手性β，β-二取代乙烯基亚砜的新合成方法。由于反应以非常高的顺选择性进行，因此通过改变1-炔基亚砜和有机锌试剂的组合来立体选择性地合成两种几何的β，β-二取代的乙烯基亚砜。
• Synthesis of Enantiopure 3-Hydroxypiperidines from Sulfinyl Dienyl Amines by Diastereoselective Intramolecular Cyclization and [2,3]-Sigmatropic Rearrangement
  作者：Carmen Simal、Robert H. Bates、Mercedes Ureña、Irene Giménez、Christina Koutsou、Lourdes Infantes、Roberto Fernández de la Pradilla、Alma Viso

  DOI：10.1021/acs.joc.5b01307

  日期：2015.8.7

  novel sulfinyl tetrahydropyridines that are readily converted to 3-hydroxy tetrahydropyridines via sigmatropic rearrangement. The influence of N- and C- substituents on the process has been studied. Procedures to shorten the sequence such as the tandem cyclization followed by [2,3]-sigmatropic rearrangement, as well as cyclization of the free amine, under Boc- or ArSO- deprotection conditions have been

  多种对映体纯的亚磺酰基二烯基胺的高度非对映选择性的碱促进的分子内环化作用提供了新颖的亚磺酰基四氢吡啶，其易于通过σ重排转化为3-羟基四氢吡啶。已经研究了N-和C-取代基对该方法的影响。在Boc-或ArSO-脱保护条件下，已经研究了缩短序列的程序，例如串联环化，然后进行[2,3]-σ重排，以及游离胺的环化。对于所报道的转化，通常观察到良好至优异的选择性水平（dr：75/25至> 98/2）。还报道了访问取代的氨基二烯亚砜的新方案。
• Synthesis and Dienophilic Behavior of Enantiomerically Pure (<i>Z</i>)-3-<i>p</i>-Tolylsulfinylacrylonitriles
  作者：Jose L. García Ruano、Antonio Esteban Gamboa、Ana M. Martín Castro、Jesús H. Rodríguez、M. Isabel López-Solera

  DOI：10.1021/jo9721002

  日期：1998.5.1

  The syntheses of enantiomerically pure (Z)-3-p-tolylsulfinylacrylonitrile (1b) and its 2-n-butyl (1a), 2-tert-butyl (1c), and 2-benzyl(ld) derivatives, by stereoselective hydrocyanation with Et2AlCN of their corresponding alkynylsulfoxides, are described. Asymmetric Diels-Alder reactions of these dienophiles with cyclopentadiene are also reported, the most significant finding being their total pi-facial diastereoselectivity, controlled by the sulfur configuration, which can be readily invented by using BF3 as a catalyst. The endo selectivity is very high for Ib under thermal and catalytic (ZnBr2) conditions and complete in the presence of BE3 whereas la and Id only exhibit a complete endo selectivity in the presence of BF3.
• (<i>Z</i>)-3-<i>p</i>-Tolylsulfinylacrylonitriles as Chiral Dipolarophiles:  Reactions with Diazoalkanes
  作者：José L. García Ruano、Sergio A. Alonso de Diego、Daniel Blanco、Ana M. Martín Castro、M. Rosario Martín、Jesús H. Rodríguez Ramos

  DOI：10.1021/ol016481o

  日期：2001.10.1

  [reaction: see text] The dipolarophilic reactivity of enantiopure (Z)-3-p-tolylsulfinylacrylonitriles (1) has been evaluated with diazoalkanes. 3-Cyanopyrazoles are obtained when R = H, but with R = alkyl (Bn, n-Bu, and t-Bu) only one cycloadduct (4 or 5) is formed in high yield under mild conditions, therefore evidencing a complete control of the regioselectivity and the endo/exo and pi-facial selectivities

  [反应：见正文]已用重氮烷评估了对映纯（Z）-3-对甲苯基亚磺酰基丙烯腈（1）的偶极亲和性。当R = H时获得3-氰基吡唑，但当R =烷基（Bn，n-Bu和t-Bu）时，在温和条件下仅以高收率形成一个环加合物（4或5），因此证明了对苯并吡咯的完全控制。区域选择性以及内/外和面部选择性。这些反应是吡唑啉及其相关结构合成的新的直接途径，并揭示了（Z）-亚磺酰基丙烯腈的优异的双亲性特征。