Novel Syntheses of Nitrogen Heterocycles from Isocyanides

The direct copper(I)-catalyzed synthesis of oligosubstituted pyrroles from substituted methyl isocyanides and acceptor-substituted acetylenes as well as copper(I)-mediated route to pyrroles from substituted methyl isocyanides and non-activated terminal acetylenes have been investigated. 2-Substituted phenyl isocyanides were obtained by trapping of generated in situ ortho-lithiophenyl isocyanide with electrophiles. This strategy has been effectively employed for the new synthesis of substituted 3H-quinazolin-4-ones (-thiones) including the naturally occurring alkaloids deoxyvasicinone and tryptanthrine. The reactions of ortho-lithiophenyl isocyanide and other ortho-lithiohetaryl isocyanides with aldehydes, ketones, and carbon dioxide have been investigated in detail. Two novel rearrangements of the intermediate 2-lithio-4H-3,1-benzoxazines have been disclosed. A novel copper-catalyzed synthesis of benzimidazoles from ortho-bromoaryl isocyanides and primary amines has been developed.

Autorentext

Alexander V. Lygin was born in 1984 in Krasnokamensk, Russia. He studied chemistry at the M.V. Lomonosov Moscow State University in 2001-2006. Later he carried out his doctoral thesis work in the group of Prof. Armin de Meijere (Göttingen, Germany) and obtained his doctoral degree (summa cum laude) in 2009.