Snieckus氨基甲酸酯重排
氨基甲酸-O-芳基酯进行邻位金属化后，氨基甲酰基由氧迁移到邻位的碳上得到邻酚基苯酰胺的反应。与Hauser–Beak反应类似。空间位置相近的位点也可以进行反应。
反应机理
反应实例
N,N-Diethyl-2-methoxy-3-carboxybenzamide (3). 1 (2.06 g, 8.7 mmol) in THF (10 mL) was added to s-BuLi (13.8 mL, 19.14 mmol) (1.39 M) and TMEDA (2.9 mL, 19.14 mmol) in THF (170 mL) under N2 at -78 ℃ with stirring. After slow heating for 12 h to 20 ℃, a 25% NH4Cl solution was added, the solvent was removed in vacuo and the residue extracted with Et2O. The aq layer was acidified, extracted with Et2O/DCM, the residue (1.7 g) was heated with MeI (10 mL) and K2CO3 (3 g) in Me2CO (30 mL) for 20 h. Chromatography (silica gel, EA:hexane 1:1) afforded 976 mg of ester which on hydrolysis (NaOH 3 g, MeOH 60 mL and water 10 mL, 24 h) gave after crystallization from DCM:hexane 84 mg of 3 (89%) mp 123–124 ℃.
【Snieckus V J Am Chem Soc 1985 107 6312】
相关文献
1 Snieckus V Heterocycles 1980 14 1649
2R Snieckus V Acc Chem Res 1982 15 306
3 Snieckus V J Org Chem 1983 48 1935
4 Snieckus V J Am Chem Soc 1985 107 6312
5R Snieckus V Chem Rev 1990 90 879
6 Snieckus V J Org Chem 1991 56 3763
7 Gawley RE J Org Chem 1993 58 3223
8 Collum DB J Am Chem Soc 2008 130 13709
编译自：Organic Syntheses Based On Name Reactions, 3RdEd, A. Hassner, Page 445-446.
相关反应