(1S)-1-methyl-2-propan-2-yl-1H-2-benzazepine-3,5-dione | 361459-13-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异喹啉及其衍生物
• 英文名称: (1S)-1-methyl-2-propan-2-yl-1H-2-benzazepine-3,5-dione
• CAS: 361459-13-4
• 化学式: C₁₄H₁₇NO₂
• 分子量: 231.294
• InChiKey: KHTLAGQXPUCFQE-JTQLQIEISA-N

物化性质

• 熔点：
  148 °C(Solv: cyclohexane (110-82-7); ethyl acetate (141-78-6))
• 沸点：
  387.3±41.0 °C(Predicted)
• 密度：
  1.100±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  37.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1S)-1-methyl-2-propan-2-yl-1H-2-benzazepine-3,5-dione 在 sodium carbonate 、 三乙胺 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 26.0h， 生成 (5S)-5,13-dimethyl-6-propan-2-yl-5H-quinolino[3,2-d][2]benzazepin-13-ium-7-one;trifluoromethanesulfonate
  参考文献：
  名称：

  Preparation of axially chiral quinolinium salts related to NAD+ models: new investigations of these biomimetic models as ‘chiral amide-transferring agents’

  摘要：

  The general purpose of this work is to investigate the potential of biomimetic NAD(+) models as 'nucleophile-transferring agents' with the ultimate motivation to develop new synthetic tools. This first report focuses on the preparation of an axially chiral quinolinium salt 8. A preliminary investigation of these NAD(+) analogues as 'chiral amide-transferring agents' is reported herein. The synthesis of the desired quinolinium salt 8 was first attempted via a Friedlander approach. Given the poor reproducibility of this first synthetic route, a second strategy making use of an intramolecular nickel-catalyzed coupling was developed with success, furnishing the quinolinium salt 8 in 12% overall yield. The potential of the quinolinium salt 8 as a 'chiral amide-transferring agent' was then investigated. Regioselective 1,4-addition of benzylamine and piperidine produced, respectively, adducts 18a and 18b with high diastereoselectivity (de >95%). The resulting 'chiral masked-amide' 18b was reacted with various activated aryl esters affording the corresponding atropisomeric amide 20 with modest atropenantioselectivity (ee = 2-20%). (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.11.004
• 作为产物：
  描述：

  (1S)-N-(1-methylethylidene)-1-phenylethylamine 在 氢氧化钾 、 sodium tetrahydroborate 、 三氯化铝 、 草酰氯 、 三乙胺 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 21.0h， 生成 (1S)-1-methyl-2-propan-2-yl-1H-2-benzazepine-3,5-dione
  参考文献：
  名称：

  Preparation of axially chiral quinolinium salts related to NAD+ models: new investigations of these biomimetic models as ‘chiral amide-transferring agents’

  摘要：

  The general purpose of this work is to investigate the potential of biomimetic NAD(+) models as 'nucleophile-transferring agents' with the ultimate motivation to develop new synthetic tools. This first report focuses on the preparation of an axially chiral quinolinium salt 8. A preliminary investigation of these NAD(+) analogues as 'chiral amide-transferring agents' is reported herein. The synthesis of the desired quinolinium salt 8 was first attempted via a Friedlander approach. Given the poor reproducibility of this first synthetic route, a second strategy making use of an intramolecular nickel-catalyzed coupling was developed with success, furnishing the quinolinium salt 8 in 12% overall yield. The potential of the quinolinium salt 8 as a 'chiral amide-transferring agent' was then investigated. Regioselective 1,4-addition of benzylamine and piperidine produced, respectively, adducts 18a and 18b with high diastereoselectivity (de >95%). The resulting 'chiral masked-amide' 18b was reacted with various activated aryl esters affording the corresponding atropisomeric amide 20 with modest atropenantioselectivity (ee = 2-20%). (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.11.004

文献信息

• Design of new axially chiral NADH mimics. Mechanistic investigation of the enantioselective hydride transfer
  作者：Jean-Luc Vasse、Georges Dupas、Jack Duflos、Guy Quéguiner、Jean Bourguignon、Vincent Levacher

  DOI：10.1016/s0040-4039(01)00805-x

  日期：2001.7

  This paper reports the design of a new axially chiral NADH model which relies on the configurational control around the C3-C-O chiral axis by means of a chiral relay installed on the cyclic structure. The conformational and configurational control of the lactam moiety was successfully achieved affording two conformational diastereoisomers (aS,S)-1 and (aR,S)-1 in a ratio of 95:5, respectively. Reduction of methyl benzoylformate with model 1 afforded (R)-methyl mandelate in up to 84% e.e. The stereoselective synthesis of 4-deuterated model 1 allowed us to establish that this enantioselective reduction arises from the migration of the syn-oriented hydrogen with regard to the carbonyl dipole. (C) 2001 Elsevier Science Ltd. All rights reserved.