Synthesis and [3,3]-Sigmatropic Rearrangement of Vinylaziridines
Sammanfattning: A general synthetic route from vinylepoxides to vinylaziridines via 1,2-amino alcohols was developed. The 1,2-amino alcohols were obtained from a stereospecific and regioselective aminolysis of vinylepoxides. The synthetic scope of the aminolysis could be expanded by the use of a microwave-assisted protocol. Some of the 1,2-amino alcohols were dehydrated with PPh3/DEAD to afford N-H vinylaziridines. All of the so obtained N-H vinylaziridines were acylated to give the corresponding N-acyl vinylaziridines. When variously substituted N-acyl vinylaziridines were subjected to LiHMDS in THF, the resulting amide enolates underwent a stereoselective aza-[3,3]-Claisen rearrangement to give mono-, di- and trisubstituted seven-membered lactams. The scope and limitations of the rearrangement were investigated. Finally, the aminolysis of vinylepoxides was applied in an asymmetric synthesis of (+)-1-deoxynojirimycin.
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