8,8-dimethyl-3-p-tolyl-2-oxa-3-aza-bicyclo[2.2.2]octan-6-one

• 分子结构分类: 有机化合物 - 苯类化合物 - N-苯基羟胺
• 英文名称: 8,8-dimethyl-3-p-tolyl-2-oxa-3-aza-bicyclo[2.2.2]octan-6-one
• 英文别名: (1R,4R)-8,8-dimethyl-3-(4-methylphenyl)-2-oxa-3-azabicyclo[2.2.2]octan-6-one
• 化学式: C₁₅H₁₉NO₂
• 分子量: 245.321
• InChiKey: RZYUEDSJFZCKJB-ZIAGYGMSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  4,4-二甲基-2-环己基-1-酮 、 对硝基甲苯 在 (S)-5-(吡咯烷-2-基)-1H-四唑 作用下， 以 乙腈 为溶剂， 反应 20.0h， 以46%的产率得到8,8-dimethyl-3-p-tolyl-2-oxa-3-aza-bicyclo[2.2.2]octan-6-one
  参考文献：
  名称：

  Diastereo- and Enantioselective Synthesis of Nitroso Diels−Alder-Type Bicycloketones Using Dienamine:  Mechanistic Insight into Sequential Nitroso Aldol/Michael Reaction and Application for Optically Pure 1-Amino-3,4-diol Synthesis

  摘要：

  This article presents complete diastereo- and highly enantioselective synthesis of nitroso Diels-Alder-type bicycloketones using dienamine. With the hydrogen bonding of two hydroxyls in the bulky binaphthol 1c, high enantioselectivities and complete diastereoselectivity are realized in 2-oxa-3-aza-bicycloketone synthesis. On the other hand, alpha,beta-unsaturated ketone can be employed as diene precursor, utilizing readily available tetrazole catalyst 3b, to provide the 3-oxa-2-aza-bicycloketones in moderate yields with complete enantioselectivities. Investigation into the reaction utilizing 2-morpholino-4,4-diphenylcyclohexadiene 2d clearly indicated that cyclization with the bulky binaphthol 1c is involved in the sequential process, the N-nitroso aldol reaction, followed by Michael addition. In addition, optically pure 1-amino-3,4-diol is synthesized from 2-oxa-3-aza-bicycloketones. Use of p-phenoxynitrosobenzene allows access to protected amino diol via cleavage of the N-Ph bond.

  DOI：

  10.1021/ja066037m