N-[(R)-2'-hydroxy-1'-phenylethyl]-(S)-1-amino-benzocyclopentane-1-carboxamide | 365527-64-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: N-[(R)-2'-hydroxy-1'-phenylethyl]-(S)-1-amino-benzocyclopentane-1-carboxamide
• CAS: 365527-64-6
• 化学式: C₁₈H₂₀N₂O₂
• 分子量: 296.369
• InChiKey: JCSXHWWAUICUHK-WMZOPIPTSA-N

反应信息

• 作为反应物：
  描述：

  N-[(R)-2'-hydroxy-1'-phenylethyl]-(S)-1-amino-benzocyclopentane-1-carboxamide 在 lead(IV) acetate 、 methyloxirane 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 4.33h， 生成 (S)-1-aminobenzocyclopentane-1-carboxylic acid
  参考文献：
  名称：

  Enantioselective synthesis of benzocyclic α,α-dialkyl-amino acids: new insight into the solvent dependent stereoselectivity of the TMSCN addition to phenylglycinol derived imines

  摘要：

  Different benzocycloalkane-1-amino-1-carboxylic acids 1a-e have been synthesized via an asymmetric Strecker reaction using (S)-alpha -methylbenzylamine and (R)-phenylglycinol as chiral auxiliaries. The Zn2+-catalyzed addition of HCN to (S)-alpha -methylbenzylamine derived ketimines of 1-tetralone (8a) and 1-benzosuberone (8b) yielded mixtures of diastereomeric aminonitriles (1S,1 'S)-10a/(1R,1 'S)-10a (10:1 ratio) and (1R,1 'S)-10b/(1S, 1 'S)-10b (56:44 ratio), respectively. These aminonitriles are converted to amino acids la,b in two steps. The addition of TMSCN to the (R)-phenylglycinol derived ketimines of 8a, 8b, 1-indanone (8c), 7-fluoro-1-tetralone (8d), 7-fluoro-1-benzosuberone (8e) yielded mixtures of diastereomeric trimethylsilylated aminonitriles (1S,1 'R)-14a-e/(1R,1 'R)-14a-e. The addition proceeded with diastereofacial selectivities ranging from 1:2.9 to 1:25. The selectivity was found to be temperature and solvent dependent. The diastereomeric ratio (dr) of aminonitriles (1S,1 'R)-14a/(1R,1 'R)-14a increased in different solvents in the order methanol < methanol/ CH2Cl2(1:2.5)< THF < toluene < CHCl3< CH2Cl2. In the pure THF, toluene, CHCl3, or CH2Cl2 kinetic product mixtures were formed, whereas the presence of methanol led to thermally equilibrated product mixtures. This solvent dependent change of the product dr is interpreted with a change in the TMSCN addition mechanism. Hydrolysis of the aminonitrile mixtures (1S,1 'R)-14a-c/(1R,1 'R)-14a-e and oxidative cleavage of the auxiliary yielded 1a-c, which showed the (S)-configuration as the major isomer. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)00505-1
• 作为产物：
  描述：

  (1,3'S)-indan-1-spiro-3'-[(5'R)-5'-phenyl-2',3',5',6'-tetrahydro-1',4'-oxazin-2'-one] 在 氨 作用下， 以 甲醇 为溶剂， 反应 24.0h， 生成 N-[(R)-2'-hydroxy-1'-phenylethyl]-(S)-1-amino-benzocyclopentane-1-carboxamide
  参考文献：
  名称：

  Enantioselective synthesis of benzocyclic α,α-dialkyl-amino acids: new insight into the solvent dependent stereoselectivity of the TMSCN addition to phenylglycinol derived imines

  摘要：

  Different benzocycloalkane-1-amino-1-carboxylic acids 1a-e have been synthesized via an asymmetric Strecker reaction using (S)-alpha -methylbenzylamine and (R)-phenylglycinol as chiral auxiliaries. The Zn2+-catalyzed addition of HCN to (S)-alpha -methylbenzylamine derived ketimines of 1-tetralone (8a) and 1-benzosuberone (8b) yielded mixtures of diastereomeric aminonitriles (1S,1 'S)-10a/(1R,1 'S)-10a (10:1 ratio) and (1R,1 'S)-10b/(1S, 1 'S)-10b (56:44 ratio), respectively. These aminonitriles are converted to amino acids la,b in two steps. The addition of TMSCN to the (R)-phenylglycinol derived ketimines of 8a, 8b, 1-indanone (8c), 7-fluoro-1-tetralone (8d), 7-fluoro-1-benzosuberone (8e) yielded mixtures of diastereomeric trimethylsilylated aminonitriles (1S,1 'R)-14a-e/(1R,1 'R)-14a-e. The addition proceeded with diastereofacial selectivities ranging from 1:2.9 to 1:25. The selectivity was found to be temperature and solvent dependent. The diastereomeric ratio (dr) of aminonitriles (1S,1 'R)-14a/(1R,1 'R)-14a increased in different solvents in the order methanol < methanol/ CH2Cl2(1:2.5)< THF < toluene < CHCl3< CH2Cl2. In the pure THF, toluene, CHCl3, or CH2Cl2 kinetic product mixtures were formed, whereas the presence of methanol led to thermally equilibrated product mixtures. This solvent dependent change of the product dr is interpreted with a change in the TMSCN addition mechanism. Hydrolysis of the aminonitrile mixtures (1S,1 'R)-14a-c/(1R,1 'R)-14a-e and oxidative cleavage of the auxiliary yielded 1a-c, which showed the (S)-configuration as the major isomer. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)00505-1