(1S,5R)-3,6,6-trimethyl-3-azabicyclo[3.1.0]hexan-2-one | 175163-99-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: (1S,5R)-3,6,6-trimethyl-3-azabicyclo[3.1.0]hexan-2-one
• CAS: 175163-99-2
• 化学式: C₈H₁₃NO
• 分子量: 139.197
• InChiKey: RIKGRGQOTPGYRV-PHDIDXHHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1S,5R)-3,6,6-trimethyl-3-azabicyclo[3.1.0]hexan-2-one 在 劳森试剂 作用下， 以 甲苯 为溶剂， 生成 (1S,5R)-3,6,6-trimethyl-3-azabicyclo[3.1.0]hexan-2-thione
  参考文献：
  名称：

  Stereochemistry and chiroptical spectra of 3-azabicyclo[3.1.0]hexan-2-ones and thiones

  摘要：

  Several optically active substituted 3-azabicyclo[3.1.0]hexan-2-ones and their thiocarbonyl analogues have been synthesized, and their circular dichroism spectra studied. The crystal structure of thiolactam 1a showed that the bicyclic skeleton of the title compounds assumes a sofa-like geometry. It is postulated that the cyclopropyl moiety and amide or thioamide group constitute an inherently chiral chromophore, helicity of which determines the Cotton effect sign corresponding to the n-pi* electronic transition. The weak pi-pi* Cotton effect of thiolactams shows opposite sign to that observed for the lowest energy excitation. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(97)00111-0
• 作为产物：
  描述：

  N-methyl-N-(3-methyl-2-buten-1-yl)diazoacetamide 在 myoglobin variant H₆₄V V₆₈G-expressing C₄₁(DE₃) E_. coli cells 作用下， 以 aq. buffer 为溶剂， 反应 16.0h， 以45%的产率得到(1S,5R)-3,6,6-trimethyl-3-azabicyclo[3.1.0]hexan-2-one
  参考文献：
  名称：

  生物催化铁催化分子内环丙烷化高选择性合成熔融环丙烷-γ-内酰胺

  摘要：

  我们报告了不对称合成的稠合环丙烷-γ-内酰胺的铁基生物催化策略的发展，这是在合成药物和生物活性天然产物中发现的关键结构图案。结合使用突变景观和迭代位点饱和诱变技术，抹香鲸肌红蛋白已发展成为一种生物催化剂，能够以高收率和高对映选择性（高达99种）促进各种烯丙基重氮乙酰胺底物环化成相应的双环内酰胺。 ％ee）。这些生物催化转化可在整个细胞中进行，并可用于使手性环丙烷-γ-内酰胺以及β-环丙胺和环丙烷稠合的吡咯烷酮高效（化学）酶促构建，

  DOI：

  10.1021/acscatal.9b05383

文献信息

• Highly Enantioselective Intramolecular Cyclopropanation Reactions of <i>N</i>-Allylic-<i>N</i>-methyldiazoacetamides Catalyzed by Chiral Dirhodium(II) Carboxamidates
  作者：Michael P. Doyle、Alexey V. Kalinin

  DOI：10.1021/jo9519219

  日期：1996.1.1

  Catalytic diazo decomposition of representative N-allylic-N-methyldiazoacetamides produced the corresponding intramolecular cyclopropanation products in good to excellent yields and with exceptional enantiocontrol. In the simplest case, with N-allyl-N-methyldiazoacetamide, catalysis by dirhodium(II) tetrakis[methyl 2-oxapyrrolidine-5(S)-carboxylate], Rh-2(5(S)-MEPY)(4), achieved the highest yield and enantioselectivity (93% eel. Dirhodium(II) tetrakis[methyl 2-oxo-1-(3-phenylpropanoyl)imidazolidin-4(S)-carboxylate] Rh-2(4S)-MPPIM)(4), was preferred for substituted N-allylic-N-methyldiazoacetamides from which 92-95% ee's were obtained in intramolecular cyclopropanation reactions (88-95% yields), even when the catalyst was employed in only 0.1 mol %, Competition with intramolecular dipolar cycloaddition was minimized with the use of N-methyldiazoacetamides relative to N-tert-butyldiazoacetamides.
• Stereochemistry and chiroptical spectra of 3-azabicyclo[3.1.0]hexan-2-ones and thiones
  作者：Maria J. Milewska、Maria Gdaniec、Tadeusz Poloński

  DOI：10.1016/s0957-4166(97)00111-0

  日期：1997.4

  Several optically active substituted 3-azabicyclo[3.1.0]hexan-2-ones and their thiocarbonyl analogues have been synthesized, and their circular dichroism spectra studied. The crystal structure of thiolactam 1a showed that the bicyclic skeleton of the title compounds assumes a sofa-like geometry. It is postulated that the cyclopropyl moiety and amide or thioamide group constitute an inherently chiral chromophore, helicity of which determines the Cotton effect sign corresponding to the n-pi* electronic transition. The weak pi-pi* Cotton effect of thiolactams shows opposite sign to that observed for the lowest energy excitation. (C) 1997 Elsevier Science Ltd.
• Highly Stereoselective Synthesis of Fused Cyclopropane-γ-Lactams via Biocatalytic Iron-Catalyzed Intramolecular Cyclopropanation
  作者：Xinkun Ren、Ajay L. Chandgude、Rudi Fasan

  DOI：10.1021/acscatal.9b05383

  日期：2020.2.7

  We report the development of an iron-based biocatalytic strategy for the asymmetric synthesis of fused cyclopropane-γ-lactams, which are key structural motifs found in synthetic drugs and bioactive natural products. Using a combination of mutational landscape and iterative site-saturation mutagenesis, sperm whale myoglobin was evolved into a biocatalyst capable of promoting the cyclization of a diverse

  我们报告了不对称合成的稠合环丙烷-γ-内酰胺的铁基生物催化策略的发展，这是在合成药物和生物活性天然产物中发现的关键结构图案。结合使用突变景观和迭代位点饱和诱变技术，抹香鲸肌红蛋白已发展成为一种生物催化剂，能够以高收率和高对映选择性（高达99种）促进各种烯丙基重氮乙酰胺底物环化成相应的双环内酰胺。 ％ee）。这些生物催化转化可在整个细胞中进行，并可用于使手性环丙烷-γ-内酰胺以及β-环丙胺和环丙烷稠合的吡咯烷酮高效（化学）酶促构建，