Synthesis of bicyclic alkaloid cores from substituted η2 pyridine complexes

ORGN 162

George William Kosturko, gwk3u@virginia.edu, Department of Chemistry, The University of Virginia, McCormick Road, Charlottesville, VA 22903
Transformation of substituted pyridines to cyclic 2-azadienes is attained through their dihapto coordination to the chiral π-basic metal complex {TpW(NO)(PMe3)}. The resulting azadiene complex is reactive toward Diels-Alder cycloadditions with various dienophiles, yielding azabicyclic scaffolds. The metal complex sets new bridgehead stereocenters generated from the cycloaddition, and isolation of one diastereomer is possible through selective precipitation. Oxidation of the organometallic fragment leads to isolation of highly functionalized isoquinuclidine skeletons, which may be further chemically elaborated.