Catalytic reduction and intramolecular cyclization of haloalkynes in the presence of nickel(I) salen electrogenerated at carbon cathodes in dimethylformamide.
[reaction: see text] Pentylidenecyclopentane can be conveniently prepared in up to 86% yield via the catalytic reduction of 1-iodo- or 1-bromo-5-decyne by [[2,2'-[1,2-ethanediylbis(nitrilomethylidyne)]bis[phenolato]]-N,N',O,O']nickelate(I) electrogenerated at a carbon cathode in dimethylformamide containing tetramethylammonium tetrafluoroborate. This electrosynthesis can be accomplished at potentials for which the haloalkynes are electroinactive, and it can be completed within 30 min at room temperature. Attempts to synthesize pentylidenecyclobutane and pentylidenecyclohexane from 1-halo-4-nonynes and 11-halo-5-undecynes, respectively, under similar conditions afford the carbocycles in very low yields (2% and 6%, respectively). Other products derived from the various haloalkynes are dimers, alkynes, and 1-alkenynes. Dimers (alkadiynes) arising from 1-halo-4-nonynes and 11-halo-5-undecynes are formed in yields ranging from 80% to 89%, whereas icosa-5,15-diyne (the dimer obtained from a 1-halo-5-decyne) is found in significantly lower yield (</=13%). Alkynes and 1-alkenynes are produced in yields of 3-10% and 2-3%, respectively. A mechanistic scheme, involving alkyn-1-yl radicals arising from nickel(I) salen catalyzed cleavage of the carbon-halogen bond of each haloalkyne, is proposed to account for the formation of all products.
Ischay
Michael A
MA
Department of Chemistry, Indiana University, Bloomington, Indiana 47405, USA.
Mubarak
Mohammad S
MS
Peters
Dennis G
DG