4-methyl-N-(3-phenylprop-2-yn-1-yl)-N-((1-vinylcyclopropyl)methyl)benzenesulfonamide | 1228437-91-9

• 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: 4-methyl-N-(3-phenylprop-2-yn-1-yl)-N-((1-vinylcyclopropyl)methyl)benzenesulfonamide
• CAS: 1228437-91-9
• 化学式: C₂₂H₂₃NO₂S
• 分子量: 365.496
• InChiKey: VIJBFSKDZXTJBD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.0
• 重原子数：
  26.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  37.38
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  一氧化碳 、 4-methyl-N-(3-phenylprop-2-yn-1-yl)-N-((1-vinylcyclopropyl)methyl)benzenesulfonamide 在 di(rhodium)tetracarbonyl dichloride 作用下， 以 甲苯 为溶剂， 80.0 ℃ 、20.27 kPa 条件下， 反应 1.0h， 以89%的产率得到4-phenyl-2-tosyl-7a-vinyl-2,3,7,7a-tetrahydro-1H-isoindol-5(6H)-one
  参考文献：
  名称：

  Rh(I)-Catalyzed [(3 + 2) + 1] Cycloaddition of 1-Yne/Ene-vinylcyclopropanes and CO: Homologous Pauson−Khand Reaction and Total Synthesis of (±)-α-Agarofuran

  摘要：

  A novel Rh(I)-catalyzed [(3 + 2) + 1] cycloaddition, which can be regarded as a homologous Pauson-Khand reaction, was developed to synthesize bicyclic cyclohexenones and cyclohexanones, enabling a new approach for synthesis of six-membered carbocycles ubiquitously found in natural products and pharmaceutics. The significance of the Rh-catalyzed [(3 + 2) + 1] cycloaddition has been demonstrated by the total synthesis of a furanoid sesquiterpene natural product, a-agarofuran, in which the bicyclic skeleton was constructed by the [(3 + 2) + 1] reaction of 1-yne-VCP and CO.

  DOI：

  10.1021/ol100625e
• 作为产物：
  描述：

  碘苯 、 N-[(1-ethenylcyclopropyl)methyl]-4-methyl-N-prop-2-ynylbenzenesulfonamide 在 copper(l) iodide 、 四(三苯基膦)钯 、 二异丙胺 作用下， 以 四氢呋喃 为溶剂， 以47%的产率得到4-methyl-N-(3-phenylprop-2-yn-1-yl)-N-((1-vinylcyclopropyl)methyl)benzenesulfonamide
  参考文献：
  名称：

  Rh(I)-Catalyzed [(3 + 2) + 1] Cycloaddition of 1-Yne/Ene-vinylcyclopropanes and CO: Homologous Pauson−Khand Reaction and Total Synthesis of (±)-α-Agarofuran

  摘要：

  A novel Rh(I)-catalyzed [(3 + 2) + 1] cycloaddition, which can be regarded as a homologous Pauson-Khand reaction, was developed to synthesize bicyclic cyclohexenones and cyclohexanones, enabling a new approach for synthesis of six-membered carbocycles ubiquitously found in natural products and pharmaceutics. The significance of the Rh-catalyzed [(3 + 2) + 1] cycloaddition has been demonstrated by the total synthesis of a furanoid sesquiterpene natural product, a-agarofuran, in which the bicyclic skeleton was constructed by the [(3 + 2) + 1] reaction of 1-yne-VCP and CO.

  DOI：

  10.1021/ol100625e

文献信息

• Asymmetric Rh(I)-Catalyzed Intramolecular [3 + 2] Cycloaddition of 1-Yne-vinylcyclopropanes for Bicyclo[3.3.0] Compounds with a Chiral Quaternary Carbon Stereocenter and Density Functional Theory Study of the Origins of Enantioselectivity
  作者：Mu Lin、Guan-Yu Kang、Yi-An Guo、Zhi-Xiang Yu

  DOI：10.1021/ja2082119

  日期：2012.1.11

  A highly enantioselective Rh(I)-catalyzed intramolecular [3 + 2] cycloaddition of 1-yne-VCPs to bicyclo[3.3.0] compounds with an all-carbon chiral quaternary stereocenter at the bridgehead carbon was developed. DFT calculations of the energy surface of the catalytic cycle (complexation, cyclopropane cleavage, alkyne insertion, and reductive elimination) of the asymmetric [3 + 2] cycloaddition reaction

  开发了一种高度对映选择性的 Rh(I) 催化分子内 [3 + 2] 环加成反应，将 1-yne-VCPs 与双环 [3.3.0] 化合物在桥头碳处具有全碳手性四元立体中心。不对称 [3 + 2] 环加成反应的催化循环（络合、环丙烷裂解、炔烃插入和还原消除）的能量表面的 DFT 计算表明，速率和立体决定步骤是炔烃插入步骤。炔烃插入过渡态的分析表明，底物的炔烃部分中的取代基与刚性 H(8)-BINAP 主链之间的严重空间排斥是不产生不受欢迎的 [3 + 2] 环加合物的原因。