2,3,5,6,7,8-hexahydro-2,3-diphenylbenzo[e][1,3]oxazin-4-one | 1276030-36-4

• 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: 2,3,5,6,7,8-hexahydro-2,3-diphenylbenzo[e][1,3]oxazin-4-one
• 英文别名: 2,3-diphenyl-5,6,7,8-tetrahydro-2H-1,3-benzoxazin-4-one
• CAS: 1276030-36-4
• 化学式: C₂₀H₁₉NO₂
• 分子量: 305.376
• InChiKey: WGTVLYAUOPUJEC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1,7-庚二酰氯 、 N-苄叉苯胺 在 三乙胺 作用下， 以 甲苯 为溶剂， 反应 3.0h， 以27%的产率得到2,3,5,6,7,8-hexahydro-2,3-diphenylbenzo[e][1,3]oxazin-4-one
  参考文献：
  名称：

  Annuloselectivity in Reactions of Diacyl Dichlorides and Imines: Combined Experimental and Theoretical Studies

  摘要：

  The annuloselectivity defined as the annulation selectivity between [2 + 2] and cascade annulations of diacyl dichlorides and imines in the presence of organic bases to afford bis-beta-lactams and 2,3-dihydro-1,3-oxazin-4-ones has been studied extensively with a combination of experiments and density functional theory (DFT) calculations. The present results indicate that it is the preference of diacyl dichlorides in the formation of cyclic alpha-oxoketenes in the presence of organic bases that controls the annuloselectivity. The cascade annulations of hexanedioyl and heptanedioyl dichlorides undergo the chloride-assisted cyclization of the corresponding omega-chlorocarbonylalkylketenes as the rate-determining step in the presence of triethylamine, rather than the generation of bisketenes followed by dimerization, affording five- and six-membered cyclic alpha-oxoketenes followed by the [4 + 2] annulations with imines to furnish 2,3-dihydro-1,3-oxazin-4-ones. This is an energetically competitive pathway to the normal Staudinger cycloaddition. Further decreasing (pentanedioyl dichloride) or increasing the linker length (octanedioyl and nonanedioyl dichlorides) results in the enhanced energetic barriers for the cyclization, which is less competitive to the direct Staudinger cycloaddition to afford bis-trans-beta-lactams as the sole products. The current results provide an insight into the annuloselective control in the reactions of diacyl dichlorides and imines.

  DOI：

  10.1021/acs.joc.5b00573

文献信息

• Pd-Catalyzed Carbonylation of Diazo Compounds at Atmospheric Pressure: A Catalytic Approach to Ketenes
  作者：Zhenhua Zhang、Yiyang Liu、Lin Ling、Yuxue Li、Yian Dong、Mingxing Gong、Xiaokun Zhao、Yan Zhang、Jianbo Wang

  DOI：10.1021/ja107351d

  日期：2011.3.30

  and affects the diastereoselectivity of the β-lactam products by assisting isomerization of the addition intermediate. On the other hand, the acylketenes generated from the Pd-catalyzed carbonylation of α-diazoketones react with imines in a formal [4 + 2] cycloaddition manner to afford 1,3-dioxin-4-one derivatives. This straightforward carbonylation provides a new approach toward highly efficient catalytic

  由于乙烯酮介导的反应在有机合成中的重要性，因此非常需要通过催化循环使卡宾羰基化。在这项研究中，基于 Pd 催化重氮化合物与 CO 的羰基化，开发了一种高效、温和的乙烯酮中间体催化方法。 当 α-重氮羰基化合物或 N-甲苯磺酰腙盐在钯催化剂存在下在常压下加热时在 CO 压力下，烯酮中间体在原位形成，在那里它们与各种亲核试剂（如醇、胺或亚胺）进行进一步反应。Pd 催化的串联羰基化-施陶丁格环加成反应以良好的产率得到 β-内酰胺衍生物，并具有优异的反式非对映选择性。反应机理的 DFT 计算结果表明，Pd 参与 [2+2] 环加成过程，并通过辅助加成中间体的异构化影响 β-内酰胺产物的非对映选择性。另一方面，由 Pd 催化的 α-重氮酮羰基化产生的酰基烯酮与亚胺以正式的 [4 + 2] 环加成方式反应，得到 1,3-dioxin-4-one 衍生物。这种直接的羰基化提供了一种在温和条件下高效催化生成烯酮物种的新方法。由