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Aza-[3,3]-Claisen Enolate Rearrangement in Vinylaziridines: Stereoselective Synthesis of Mono-, Di-, and Trisubstituted Seven-Membered Lactams

2001; Wiley; Volume: 7; Issue: 1 Linguagem: Inglês

10.1002/1521-3765(20010105)7

1521-3765

Ulf M. Lindström, Peter Somfai,

Asymmetric Synthesis and Catalysis

Several 2,3-disubstituted vinylaziridines have been N-acylated and subjected to LiHMDS in THF at −78 °C. Upon warming to room temperature, the resulting amide enolates underwent a highly stereoselective [3,3]-sigmatropic rearrangement to give mono-, di-, and trisubstituted seven-membered lactams in good yields. The scope and limitations of the process have been investigated by using variously substituted vinylaziridines. A kinetically controlled process proceeding through a six-membered boatlike transition state assembly has been invoked to explain the stereochemical outcome of the reaction.