trans-N-(p-Toluenesulfonyl)-4-phenyl-5-vinyl-6-aza-2-oxacyclohexan-1-one | 145198-92-1

• 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: trans-N-(p-Toluenesulfonyl)-4-phenyl-5-vinyl-6-aza-2-oxacyclohexan-1-one
• 英文别名: trans-5-phenyl-3-p-toluenesulfonyl-4-vinyl-1,3-oxazin-2-one；(4R,5R)-4-ethenyl-3-(4-methylphenyl)sulfonyl-5-phenyl-1,3-oxazinan-2-one
• CAS: 145198-92-1
• 化学式: C₁₉H₁₉NO₄S
• 分子量: 357.43
• InChiKey: NNTRQLQWMHYCDB-QZTJIDSGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  72.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  对甲基苯磺酰异氰酸酯 、 5-Phenyl-4-vinyl-[1,3]dioxan-2-one 在 四(三苯基膦)钯 作用下， 以 1,4-二氧六环 为溶剂， 反应 1.0h， 以66%的产率得到trans-N-(p-Toluenesulfonyl)-4-phenyl-5-vinyl-6-aza-2-oxacyclohexan-1-one
  参考文献：
  名称：

  Palladium-catalysed regio- and stereo-selective synthesis of allylic amines

  摘要：

  3-乙烯基-2,6-二氧杂环己烷-1-酮 1 经 N-对甲基苯磺酰或 N-芳基异氰酸酯和催化量的 Pd0 处理后，以良好的收率和独特的立体选择性转化为 N-对甲基苯磺酰和 N-芳基-3-乙烯基-2-氮杂-6-氧杂环己烷-1-酮 2。

  DOI：

  10.1039/c39920001498

文献信息

• Striking AcOH Acceleration in Direct Intramolecular Allylic Amination Reactions
  作者：Fady Nahra、Frédéric Liron、Guillaume Prestat、Carlo Mealli、Abdelatif Messaoudi、Giovanni Poli

  DOI：10.1002/chem.200901946

  日期：2009.10.26

  An acid–base reaction to speed up a sluggish catalytic cycle! AcOH as the solvent enables extraordinarily fast and efficient PdII‐catalysed, direct intramolecular allylic aminations, assisting the benzoquinone‐mediated palladium reoxidation and ionisation of the intermediate palladium complexes (see scheme). The structural and energetic aspects of such a key step of the catalytic cycle are illustrated

  酸碱反应可加快缓慢的催化循环！以乙酸为溶剂，可实现快速，有效的Pd II催化的直接分子内烯丙基胺化反应，协助苯醌介导的钯的再氧化和中间钯配合物的电离（参见方案）。通过详细的DFT分析说明了催化循环中这一关键步骤的结构和能量方面。
• Palladium-catalysed regio- and stereo-selective synthesis of allylic amines
  作者：Yoshinao Tamaru、Takashi Bando、Youichi Kawamura、Kazuto Okamura、Zen-ichi Yoshida、Motoo Shiro

  DOI：10.1039/c39920001498

  日期：——

  3-Vinyl-2,6-dioxacyclohexan-1-ones 1, by treatment with N-tosyl or N-aryl isocyanates and a catalytic amount of Pd0, are converted into N-tosyl- and N-aryl-3-vinyl-2-aza-6-oxacyclohexan-1-ones 2 in good yields and with unique stereoselectivity.

  3-乙烯基-2,6-二氧杂环己烷-1-酮 1 经 N-对甲基苯磺酰或 N-芳基异氰酸酯和催化量的 Pd0 处理后，以良好的收率和独特的立体选择性转化为 N-对甲基苯磺酰和 N-芳基-3-乙烯基-2-氮杂-6-氧杂环己烷-1-酮 2。
• Regio- and Stereoselective Synthesis of 1,3-Hydroxyl Amines via Palladium-Catalyzed Carbonate-Carbamate Transformation with Unique Stereoselectivity: Synthesis of 3-Amino-4-penten-1-ols
  作者：Takashi Bando、Hiroto Harayama、Yoshimasa Fukazawa、Motoo Shiro、Keigo Fugami、Shuji Tanaka、Yoshinao Tamaru

  DOI：10.1021/jo00085a039

  日期：1994.3

  The transformation of cyclic carbonates 1 to cyclic carbamates 4 is achieved in the presence of aryl or sulfonyl isocyanate by the catalysis of Pd(0) in high yield and with high structural flexibility. The reaction shows unique stereoselectivity: 3,4-disubstituted carbonates 2, irrespective of the composition of their stereoisomers, provide trans-5 exclusively or predominantly over cis-5. Mixtures of cis- and trans-3,5-disubstituted carbonates 3 furnish either cis-6 or trans-6 in high selectivity depending on the reaction conditions (kinetic or thermodynamic control, respectively). H-1 NMR and X-ray structure analyses of 5 and 6 indicate that the stereochemical outcome is governed by an A1,2-strain between N-sulfonyl and C5-vinyl substituents.