(3R,9aR)-9a-Methyl-3-phenyl-2,3,9,9a-tetrahydro-8H-oxazolo[3,2-a]azepin-5-one | 331993-91-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吖庚因类
• 英文名称: (3R,9aR)-9a-Methyl-3-phenyl-2,3,9,9a-tetrahydro-8H-oxazolo[3,2-a]azepin-5-one
• 英文别名: (3R,9aR)-9a-methyl-3-phenyl-2,3,8,9-tetrahydro-[1,3]oxazolo[3,2-a]azepin-5-one
• CAS: 331993-91-0
• 化学式: C₁₅H₁₇NO₂
• 分子量: 243.305
• InChiKey: VIHJMCNSVFGDII-DZGCQCFKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3R,9aR)-9a-Methyl-3-phenyl-2,3,9,9a-tetrahydro-8H-oxazolo[3,2-a]azepin-5-one 在 palladium dihydroxide 氢气 作用下， 以 乙醇 为溶剂， 反应 24.0h， 以99%的产率得到(3R,9aR)-9a-Methyl-3-phenyl-hexahydro-oxazolo[3,2-a]azepin-5-one
  参考文献：
  名称：

  Asymmetric Synthesis of 2-Alkyl-Perhydroazepines from [5,3,0]-Bicyclic Lactams

  摘要：

  The synthesis and utility of a novel class of [5,3,0]-bicyclic lactams are described. Produced by the cyclodehydration of (R)-phenylglycinol with omega -keto acids, lactams 4-6 were obtained as separable diastereomeric mixtures (similar to2:1) in low yields (similar to 40%). Higher chemical yield (up to 61%) was realized tia an alternate route involving ring closure metathesis of 2-allyl-N-acroyl oxazolidines, 8. Stereoselective reductions of the syn-bicyclic lactams, 4a and 5a, occurred with the use of alane or lithiumaluminum hydride, affording azepine alcohols, 11a and;15a, of the R configuration at the 2-position, in good to moderate yields (50-88%). High selectivity was also observed in the diisobutylaluminum hydride reduction of the epimeric anti lactams, 4b and 5b, affording azepine alcohols, 11b and 15b, of the S configuration at C-2. Hydrogenolytic cleavage of the N-benzyl moiety afforded chiral 2-substituted perhydroazepines, (R)- and (S)-12, in good yields and good enantiomeric excesses (84-94%).

  DOI：

  10.1021/jo001548r
• 作为产物：
  描述：

  5-已烯-2-酮 在 Cy₂Ru(PPh₃)2CHPh 三乙胺 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 603.0h， 生成 (3R,9aR)-9a-Methyl-3-phenyl-2,3,9,9a-tetrahydro-8H-oxazolo[3,2-a]azepin-5-one
  参考文献：
  名称：

  Asymmetric Synthesis of 2-Alkyl-Perhydroazepines from [5,3,0]-Bicyclic Lactams

  摘要：

  The synthesis and utility of a novel class of [5,3,0]-bicyclic lactams are described. Produced by the cyclodehydration of (R)-phenylglycinol with omega -keto acids, lactams 4-6 were obtained as separable diastereomeric mixtures (similar to2:1) in low yields (similar to 40%). Higher chemical yield (up to 61%) was realized tia an alternate route involving ring closure metathesis of 2-allyl-N-acroyl oxazolidines, 8. Stereoselective reductions of the syn-bicyclic lactams, 4a and 5a, occurred with the use of alane or lithiumaluminum hydride, affording azepine alcohols, 11a and;15a, of the R configuration at the 2-position, in good to moderate yields (50-88%). High selectivity was also observed in the diisobutylaluminum hydride reduction of the epimeric anti lactams, 4b and 5b, affording azepine alcohols, 11b and 15b, of the S configuration at C-2. Hydrogenolytic cleavage of the N-benzyl moiety afforded chiral 2-substituted perhydroazepines, (R)- and (S)-12, in good yields and good enantiomeric excesses (84-94%).

  DOI：

  10.1021/jo001548r

文献信息

• Asymmetric Synthesis of 2-Alkyl-Perhydroazepines from [5,3,0]-Bicyclic Lactams
  作者：A. I. Meyers、Susan V. Downing、Michael J. Weiser

  DOI：10.1021/jo001548r

  日期：2001.2.1

  The synthesis and utility of a novel class of [5,3,0]-bicyclic lactams are described. Produced by the cyclodehydration of (R)-phenylglycinol with omega -keto acids, lactams 4-6 were obtained as separable diastereomeric mixtures (similar to2:1) in low yields (similar to 40%). Higher chemical yield (up to 61%) was realized tia an alternate route involving ring closure metathesis of 2-allyl-N-acroyl oxazolidines, 8. Stereoselective reductions of the syn-bicyclic lactams, 4a and 5a, occurred with the use of alane or lithiumaluminum hydride, affording azepine alcohols, 11a and;15a, of the R configuration at the 2-position, in good to moderate yields (50-88%). High selectivity was also observed in the diisobutylaluminum hydride reduction of the epimeric anti lactams, 4b and 5b, affording azepine alcohols, 11b and 15b, of the S configuration at C-2. Hydrogenolytic cleavage of the N-benzyl moiety afforded chiral 2-substituted perhydroazepines, (R)- and (S)-12, in good yields and good enantiomeric excesses (84-94%).