(R,Z)-2-t-butyl-4-[(R)-p-tolylsulfinyl]-4,5-dihydro-3H-pyrazole-3-carbonitrile | 205251-18-9

• 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,Z)-2-t-butyl-4-[(R)-p-tolylsulfinyl]-4,5-dihydro-3H-pyrazole-3-carbonitrile
• 英文别名: (Z)-2-tert-butyl-3-[(R)-p-tolylsulfinyl]propenonitrile；(2Z)-3,3-dimethyl-2-[[(R)-(4-methylphenyl)sulfinyl]methylidene]butanenitrile
• CAS: 205251-18-9
• 化学式: C₁₄H₁₇NOS
• 分子量: 247.361
• InChiKey: FUZKOIYHMQXWGL-DPCFLFMUSA-N

物化性质

• 沸点：
  422.406±38.00 °C(Press: 760.00 Torr)(predicted)
• 密度：
  1.130±0.10 g/cm3(Temp: 25 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  60.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  重氮乙烷 、 (R,Z)-2-t-butyl-4-[(R)-p-tolylsulfinyl]-4,5-dihydro-3H-pyrazole-3-carbonitrile 以 乙醚 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 以 甲苯 为溶剂， 反应 5.5h， 生成 (R,Z)-2-t-butyl-4-[(R)-p-tolylsulfinyl]-4,5-dihydro-3H-pyrazole-3-carbonitrile
  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

• Asymmetric Synthesis of Pyrrolo[2,1-<i>a</i>]isoquinoline Derivatives by 1,3-Dipolar Cycloadditions of Stabilized Isoquinolinium<i>N</i>-Ylides with Sulfinyl Dipolarophiles
  作者：José Luis García Ruano、Alberto Fraile、M. Rosario Martín、Gemma González、Cristina Fajardo、Ana María Martín-Castro

  DOI：10.1021/jo200191c

  日期：2011.5.6

  Enantiomerically pure pyrrolo[2,1-a]isoquinoline derivatives are obtained by 1,3-dipolar reactions of isoquinolinium azomethine ylides with enantiopure 3-p-tolylsulfinylacrylonitriles, tert-butyl (2E)-4,4-diethoxy-2-p-tolylsulfinylbut-2-enoate, and 5-ethoxy-3-p-tolylsulfinylfuran-2(5H)-ones. Reactions evolve through the anti conformation of the ylide with complete regioselectivity. The facial selectivity is completely controlled by the configuration of the sulfinyl sulfur for acyclic dipolarophiles, whereas it is high (dr 83/17 or 89/11) but controlled by the C-5 configuration for sulfinylfuranones. Complete endo selectivity is observed with cyclic dipolarophiles and substituted acrylonitriles, but it is low with butenoate. The sulfinyl group also exerts a positive influence on the dipolarophilic reactivity toward these ylides.
• 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。