Frankel-Shibasaki酚丙胺重排反应

铬甲醇【Cr(CO)3】下，烯丙胺立体功能性的芳基为烯胺的中间体。中间体常以的溶剂是萘。标量二烯丙胺则发生1,5-H移入得到标量烯胺。

另外Noyori顺式甲醇剂甲醇下烯丙胺可以芳基为顺式烯胺。

中间体机理

中间体操作

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】

之外文献

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.