8,12-dioxaspiro-3-phenyl-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: 8,12-dioxaspiro-3-phenyl-2-oxa-3-aza-bicyclo[2.2.2]octan-6-one
• 英文别名: (1'R,4'R)-3'-phenylspiro[1,3-dioxolane-2,8'-2-oxa-3-azabicyclo[2.2.2]octane]-6'-one
• 化学式: C₁₄H₁₅NO₄
• 分子量: 261.277
• InChiKey: SXDLFJCWWSJOQA-CHWSQXEVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  48
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  1,4-二氧杂螺[4.5]癸-6-烯-8-酮 、 亚硝基苯 在 C₁₁H₂₃NO₃Si 作用下， 以 二甲基亚砜 为溶剂， 反应 6.0h， 以56%的产率得到8,12-dioxaspiro-3-phenyl-2-oxa-3-aza-bicyclo[2.2.2]octan-6-one
  参考文献：
  名称：

  用于不对称合成的高活性4-甲氧基脯氨酸催化剂

  摘要：

  反式-4-叔丁基二甲基甲硅烷氧基L-脯氨酸显示出比母体脯氨酸更大的催化活性，而不损害对映选择性，这扩大了羰基化合物以及O-亚硝基-醛醇/ Michael的α-氨基羟化反应中的底物范围，和曼尼希反应。

  DOI：

  10.1002/adsc.200404166

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.