Selective C-H activation alpha to primary amines. Bridging metallaaziridines for catalytic, intramolecular alpha-alkylation.
Selective alpha-C-H activation results in the synthesis of the first bridging metallaaziridine complex for the catalytic alpha-alkylation of primary amines. Reaction development led to the preparation of new Zr 2-pyridonate complexes for this useful transformation. No nitrogen protecting groups are required for this reaction, which is capable of assembling quaternary chiral centers alpha to nitrogen. Preliminary mechanistic investigations suggest bridging metallaaziridine species are the catalytically active intermediates for this alpha-functionalization reaction, while monomeric imido complexes furnish azepane hydroamination products.
Bexrud
Jason A
JA
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, B.C, Canada, V6T 1Z1.
Eisenberger
Patrick
P
Leitch
David C
DC
Payne
Philippa R
PR
Schafer
Laurel L
LL
D000475:Alkenes / Q000737:chemistry*; D000478:Alkylation; D000588:Amines / Q000138:chemical synthesis* / Q000737:chemistry; D001388:Aziridines / Q000138:chemical synthesis*; D002384:Catalysis; D006844:Hydrocarbons, Cyclic / Q000138:chemical synthesis*; D014025:Titanium / Q000737:chemistry
D000475:Alkenes; D000588:Amines; D001388:Aziridines; D006844:Hydrocarbons, Cyclic; D014025:Titanium