7,7-dimethyl-3-phenyl-2-oxa-3-aza-bicyclo[2.2.2]octan-5-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: 7,7-dimethyl-3-phenyl-2-oxa-3-aza-bicyclo[2.2.2]octan-5-one
• 英文别名: (1R,4R)-7,7-dimethyl-3-phenyl-2-oxa-3-azabicyclo[2.2.2]octan-5-one
• 化学式: C₁₄H₁₇NO₂
• 分子量: 231.294
• InChiKey: LUZHIZPQWHXAJX-DGCLKSJQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  亚硝基苯 、 4-(4,4-Dimethylcyclohexa-1,5-dien-1-yl)morpholine 在 S-1,1'-联-2-萘酚 盐酸 作用下， 以 二氯甲烷 、 正戊烷 、 四氢呋喃 为溶剂， 反应 12.0h， 生成 7,7-dimethyl-3-phenyl-2-oxa-3-aza-bicyclo[2.2.2]octan-5-one 、 7,7-dimethyl-3-phenyl-2-oxa-3-aza-bicyclo[2.2.2]octan-5-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

文献信息

• 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
  作者：Norie Momiyama、Yuhei Yamamoto、Hisashi Yamamoto

  DOI：10.1021/ja066037m

  日期：2007.2.1

  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.