Organocatalytic Synthesis of Methylene-Bridged N-Heterobiaryls.
A one-step synthesis of 1,1'- and 2,2'-methylene-bridged N-heterobiaryls directly from the corresponding N-heterocycles in a reaction with methylmagnesium chloride in the presence of catalytic amounts of N,N,N',N'-tetramethylethylenediamine under thermal and microwave conditions is reported. The split-and-merge methylenation of 2,2'-N-heterobiaryls and the direct ortho-alkylation of quinoline and isoquinoline with Grignard reagents have also been developed. Mechanistic studies identified several intermediates and provided insight into the formation and roles of magnesium hydride species in the process.
Department of Chemistry, The University of Texas at San Antonio , San Antonio, Texas 78249, United States.
David E
DE
Stephens
Department of Chemistry, The University of Texas at San Antonio , San Antonio, Texas 78249, United States.
Vu T
VT
Nguyen
Department of Chemistry, The University of Texas at San Antonio , San Antonio, Texas 78249, United States.
Bhuwan
B
Chhetri
Department of Chemistry, The University of Texas at San Antonio , San Antonio, Texas 78249, United States.
Emily R
ER
Clark
Department of Chemistry, The University of Texas at San Antonio , San Antonio, Texas 78249, United States.
Hadi D
HD
Arman
Department of Chemistry, The University of Texas at San Antonio , San Antonio, Texas 78249, United States.
Oleg V
OV
Larionov
D002384:Catalysis; D060326:Chemistry Techniques, Synthetic / Q000379:methods*; D005029:Ethylenediamines / Q000737:chemistry*; D006572:Heterocyclic Compounds, Bridged-Ring / Q000138:chemical synthesis* / Q000737:chemistry; D007546:Isoquinolines / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure
D005029:Ethylenediamines; D006572:Heterocyclic Compounds, Bridged-Ring; D007546:Isoquinolines; C005798:N,N,N',N'-tetramethylethylenediamine