Synthesis of N,N-bis(3-butenyl)amines from 2-azaallyl dication synthetic equivalents and conversion to 2,3,6,7-tetrahydroazepines by ring-closing metathesis.
N,N-Bis(3-butenyl)amines can be prepared by the double allylation of either (2-azaallyl)stannanes or (2-azaallyl)nitriles, both of which thereby act as synthetic equivalents to amine alpha,alpha'-dications (2-azaallyl dications). Allylmagnesium bromide is the reagent of choice for the double allylation of both substrates, although allyllithium also effects the double allylation of (2-azaallyl)nitriles. Ring-closing metathesis can be performed on the N-protected amines, or with in situ protonation, on the free amines to provide 2,3,6,7-tetrahydroazepines. (2-Azaallyl)nitriles can also be monoallylated to provide N-(3-butenyl)aminonitriles, whereas the double allylation of (2-azaallyl)stannanes cannot be stopped at monoallylation. (2-Azaallyl)silanes undergo monoallylation to give N-(3-butenyl)aminosilanes but do not undergo double allylation.
Pearson
William H
WH
Department of Chemistry, The University of Michigan, Ann Arbor, Michigan, 48109-1055, USA. wpearson@berryassoc.com
Aponick
Aaron
A
Dietz
Amber L
AL
D000588:Amines / Q000138:chemical synthesis*; D001381:Azepines / Q000138:chemical synthesis*; D003500:Cyclization; D009570:Nitriles / Q000737:chemistry; D017971:Tin Compounds / Q000737:chemistry
D000588:Amines; D001381:Azepines; D009570:Nitriles; D017971:Tin Compounds; C031525:stannane