(1R,4R)-8,8-dimethyl-3-phenyl-2-oxa-3-azabicyclo[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: (1R,4R)-8,8-dimethyl-3-phenyl-2-oxa-3-azabicyclo[2.2.2]octan-6-one
• 化学式: C₁₄H₁₇NO₂
• 分子量: 231.294
• InChiKey: FXBJGTRLEBAEOD-CHWSQXEVSA-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

• 作为反应物：
  描述：

  (1R,4R)-8,8-dimethyl-3-phenyl-2-oxa-3-azabicyclo[2.2.2]octan-6-one 在 sodium tetrahydroborate 作用下， 生成 (1R,4R,6R)-8,8-Dimethyl-3-phenyl-2-oxa-3-aza-bicyclo[2.2.2]octan-6-ol
  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
• 作为产物：
  描述：

  4,4-二甲基-2-环己基-1-酮 、 亚硝基苯 在 C₁₁H₂₃NO₃Si 作用下， 以 二甲基亚砜 为溶剂， 反应 0.5h， 以76%的产率得到(1R,4R)-8,8-dimethyl-3-phenyl-2-oxa-3-azabicyclo[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

• Novel organic catalysts for the direct enantioselective α-oxidation of carbonyl compounds
  作者：Henrik Sundén、Nils Dahlin、Ismail Ibrahem、Hans Adolfsson、Armando Córdova

  DOI：10.1016/j.tetlet.2005.03.085

  日期：2005.5

  The proline-derived N-sulfonylcarboxamide-catalyzed direct enantioselective alpha-oxidation of ketones and aldehydes with nitrosobenzene is presented. The reactions proceed smoothly furnishing the corresponding alpha-aminoxylated compounds in good yields with up to > 99% ee. The proline-derived N-sulfonylcarboxamides were also found to be excellent catalysts for the direct enantioselective nitroso Diels-Alder-type reaction between nitrosobenzene and of alpha,beta-unsaturated cyclic ketones yielding the corresponding bicyclic Diels-Alder adduct products with tip to > 99% ee. The proline-derived N-sulfonylcarboxamides represent a readily available and highly modular novel type of organic catalyst. (c) 2005 Elsevier Ltd. All rights reservesd.
• 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.