Frankel-Shibasaki烯丙胺重排反应

铬催化【Cr(CO)3】下，烯丙胺立体选择性的重排为烯胺的反应。反应常用的溶剂是萘。共轭二烯丙胺则发生1,5-H迁移得到共轭烯胺。

另外Noyori手性催化剂催化下烯丙胺可以重排为手性烯胺。

反应机理

反应操作

Methyl N-(E)-5-(methoxycarbonylpentenyl)-N-(1E,3Z)-pentadienyl carbamate (5). A mixture of diene 4 (26.9 mg, 0.1 mmol), Cr(CO)3 (2.72 mg, 0.02 mmol), naphthalene and Me2CO (1 mL) was degassed through four freeze-thaw pump cycles, stirred for 4 h at 20 C and concentrated. Silica

gel chromatography afforded 23.1 mg of 5 (86%).

【Shibasaki M, J Org Chem, 1991, 56, 4569】

相关文献

1 Frankel EN J Am Chem Soc 1968 90 2446

2 Frankel EN Tet Lett 1968 9 1919

3 Shibasaki M Chem Lett 1984 13 579

4 Shibasaki M J Am Chem Soc 1990 112 4906

5 Noyori R J Am Chem Soc 1990 112 4897

6 Noyori R Acc Chem Res 1990 23 345

7 Shibasaki M J Org Chem 1991 56 4569

8 Shibasaki M Synthesis 1993 643

9 Serebryakov EP Russ Chem Bull Int 2002 51 1341

编译自：Organic Syntheses Based On Name Reactions, 3RdEd, A. Hassner, Page 163.