N-tert-Butyl-4-formylbutanamide | 132565-60-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: N-tert-Butyl-4-formylbutanamide
• 英文别名: N-tert-butyl-5-oxopentanamide
• CAS: 132565-60-7
• 化学式: C₉H₁₇NO₂
• 分子量: 171.239
• InChiKey: IYHOHPLOKHWXIK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  46.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  一氧化碳 、 N-tert-Butyl-3-butenamide 在 三(三苯基膦)羰基氢化铑 氢气 作用下， 以 四氢呋喃 为溶剂， 100.0 ℃ 、8.27 MPa 条件下， 反应 18.0h， 以5%的产率得到N-tert-Butyl-3,4-dihydro-2-pyridone
  参考文献：
  名称：

  New synthesis of nitrogen heterocycles through amide-directed hydrocarbonylation of alkenamides catalyzed by rhodium complexes

  摘要：

  Amide-directed hydrocarbonylation of 3-butenamide (1) catalyzed by rhodium complexes such as RhCl(PPh3)3, RhCl(CO)(PPh3)2, HRh(CO)(PPh3)3, and Rh4(CO)12 gives a mixture of 3,4-dihydro-2-pyridone (2), 4-methyl-3-pyrrolin-2-one (3), and a unique heterodimer, 6-(4-methyl-2-oxo-3-pyrrolin-1-yl)-2-piperidone (4). Dihydropyridone (2) is obtained in 88% yield with 98% selectivity by using HRh(CO)(PPh)3-dppb (2 equiv) catalyst system while 4 is yielded in 90% yield with 94% selectivity with the use of RhCl(PPh3)3-P(OPh)3 (10 equiv) as the catalyst. Control experiments revealed that this crossed coupling only proceeds in the copresence of rhodium catalyst, carbon monoxide, and hydrogen. The reactions of N-benzyl-3-butenamide (1a) gives a mixture of 1-benzyldihydropyridone (2a), 1-benzyl-4-methylpyrrolinone (3a), and 1-benzyl-6-formyl-3,4-dihydropyridone (5) and its 5-formyl isomer (6). The formation of 5 and 6 is suppressed by the addition of PPh3, and 2a is selectively isolated (72%) in the reaction using RhCl(CO)(PPh3)2-PPh3 (20 equiv) as the catalyst. The hydroformylation of 2a catalyzed by RhCl(PPh3)3 gives 5 in 80% isolated yield. The reaction of N-tert-butyl-3-butenamide (1b) gives a nearly 1:1 mixture of 1-tert-butyl-4-methylpyrrolinone (3b) and uncyclized N-tert-butyl-4-formylbutanamide (7) accompanied by a small amount of 1-tert-butyldihydropyridone (2b). In the reaction of N-trityl-3-butenamide (1c), no dihydropyridone (2c) was formed, and a mixture of 1-trityl-4-methylpyrrolinone (3c) (major) and N-trityl-4-formylbutanamide (8) (minor) is yielded. The reaction of 4-pentenamide gives 4-methyl-3,4-dihydro-2-pyridone (9) exclusively regardless of the structure of the rhodium catalysts used. Possible mechanisms for these reactions are discussed.

  DOI：

  10.1021/jo00006a013

文献信息

• New synthesis of nitrogen heterocycles through amide-directed hydrocarbonylation of alkenamides catalyzed by rhodium complexes
  作者：Iwao Ojima、Anna Korda、William R. Shay

  DOI：10.1021/jo00006a013

  日期：1991.3

  Amide-directed hydrocarbonylation of 3-butenamide (1) catalyzed by rhodium complexes such as RhCl(PPh3)3, RhCl(CO)(PPh3)2, HRh(CO)(PPh3)3, and Rh4(CO)12 gives a mixture of 3,4-dihydro-2-pyridone (2), 4-methyl-3-pyrrolin-2-one (3), and a unique heterodimer, 6-(4-methyl-2-oxo-3-pyrrolin-1-yl)-2-piperidone (4). Dihydropyridone (2) is obtained in 88% yield with 98% selectivity by using HRh(CO)(PPh)3-dppb (2 equiv) catalyst system while 4 is yielded in 90% yield with 94% selectivity with the use of RhCl(PPh3)3-P(OPh)3 (10 equiv) as the catalyst. Control experiments revealed that this crossed coupling only proceeds in the copresence of rhodium catalyst, carbon monoxide, and hydrogen. The reactions of N-benzyl-3-butenamide (1a) gives a mixture of 1-benzyldihydropyridone (2a), 1-benzyl-4-methylpyrrolinone (3a), and 1-benzyl-6-formyl-3,4-dihydropyridone (5) and its 5-formyl isomer (6). The formation of 5 and 6 is suppressed by the addition of PPh3, and 2a is selectively isolated (72%) in the reaction using RhCl(CO)(PPh3)2-PPh3 (20 equiv) as the catalyst. The hydroformylation of 2a catalyzed by RhCl(PPh3)3 gives 5 in 80% isolated yield. The reaction of N-tert-butyl-3-butenamide (1b) gives a nearly 1:1 mixture of 1-tert-butyl-4-methylpyrrolinone (3b) and uncyclized N-tert-butyl-4-formylbutanamide (7) accompanied by a small amount of 1-tert-butyldihydropyridone (2b). In the reaction of N-trityl-3-butenamide (1c), no dihydropyridone (2c) was formed, and a mixture of 1-trityl-4-methylpyrrolinone (3c) (major) and N-trityl-4-formylbutanamide (8) (minor) is yielded. The reaction of 4-pentenamide gives 4-methyl-3,4-dihydro-2-pyridone (9) exclusively regardless of the structure of the rhodium catalysts used. Possible mechanisms for these reactions are discussed.