Dimerization and Isomerization Reactions of α-Lithiated Terminal Aziridines
| Autor: | Philip G. Humphreys, John G. Ward, Christopher A. J. Brierley, David M. Hodgson, Steven M. Miles |
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| Rok vydání: | 2007 |
| Předmět: |
Cyclopropanes
chemistry.chemical_classification Molecular Structure Chemistry Cyclopropanation Stereochemistry Alkene Aziridines Organic Chemistry Regioselectivity Esters Stereoisomerism Lithium Chemical synthesis Deprotonation Organometallic Compounds Stereoselectivity Amines Protecting group Dimerization Isomerization |
| Zdroj: | The Journal of Organic Chemistry. 72:10009-10021 |
| ISSN: | 1520-6904 0022-3263 |
| DOI: | 10.1021/jo701901t |
| Popis: | The scope of dimerization and isomerization reactions of alpha-lithiated terminal aziridines is detailed. Regio- and stereoselective deprotonation of simple terminal aziridines with lithium 2,2,6,6-tetramethylpiperidide (LTMP) or lithium dicyclohexylamide (LiNCy2) generates trans-alpha-lithiated terminal aziridines. These latter species can then undergo dimerization or isomerization reactions depending on the nature of the N-protecting group. alpha-Lithiated terminal aziridines bearing N-alkoxycarbonyl (Boc) protection undergo N- to C-[1,2] migration to give N-H trans-aziridinylesters. In contrast, aziridines bearing N-organosulfonyl [tert-butylsulfonyl (Bus)] protection undergo rapid dimerization to give 2-ene-1,4-diamines or, if a pendant alkene is present, diastereoselective cyclopropanation to give 2-aminobicyclo[3.1.0]hexanes. All of these reactions were used as key steps in the preparation of synthetically and biologically important targets. |
| Databáze: | OpenAIRE |
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