from first principles PP-I-1

PP-II-20A New Nitrogen-Containing Derivatives of Diterpenic Acidsin Asymmetric CatalysisKonev V.N., Khlebnikova T.B., Pai Z.P.Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russiakonevv@catalysis.ruA prospective approach to the synthesis of optically pure compounds is a modification ofnatural compounds, including terpenes having chiral centers in its structure. Abietic andlevopimaric acids are natural tricyclic diterpenes and main constituents of resin acids mixtureof the Pinus Silvestris galipot. Besides, abietic acid is the main component of colophony.In our earlier work we have developed the synthetic routes to optically pure amines, Schiffbases and ureas starting from dehydroabietic acid[1]. Further investigations in this arearesulted in the development of the new chiral diamine (2) – a diastereomerically purederivative of fumaropimaric acid. When heated with fumaric acid, methyl ester of levopimaricacid formed methylfumaropimarate, which was further transformed stereospecifically into thediamine 2 by Curtius reaction [2]. Further interaction of the resulting diamine 2 with variousaldehydes led to the formation of imines, which were reduced with sodium borohydride to thecorresponding diamines 3-6.2, R = HRNHNHRCOOCH 3 COOCH 31 2-63, R=CH 25, R=HO4, R= CH 2 6, R=SNCH 2CH 2The synthesized new chiral nitrogen containing compounds were used as organocatalysts andligands for metallocomplex catalysts of asymmetric reactions of oxidation and carbon-carbonbond forming.References:[1] T.B. Khlebnikova, N.N. Karpyshev, O.V. Tolstikova, A.G. Tolstikov, Chirality. 16 (2004) 40.[2] V.N. Konev, T.B. Khlebnikova, Z.P. Pai, Chem. for Sustainable Development. 2 (2011) 165.151