A chiral C 2 -symmetric 1,2-diamine based on a 1,1Ј-bi(tetrahydroisoquinoline) scaffold was found to be an efficient ligand for the enantioselective Ni II -catalysed Michael addition of malonic esters to conjugated nitroalkenes. The reactions proceed with 92-99 % yield and 91-99 % enantioselectivity

SummaryA number of 4-aryl- and 4-alkynyl-substituted 6H-1,2-oxazines 8 and 9 have been prepared in good yields via cross coupling reactions of halogenated precursors 2, which in turn are easily accessible by bromination of 6H-1,2-oxazines 1. Lewis-acid promoted reaction of 1,2-oxazine 9c with 1-hexyne provided alkynyl-substituted pyridine derivative 12 thus demonstrating the potential of this approach for the synthesis of pyridines.

Chiral 1,1'-Bi(tetrahydroisoquinoline)-Type Diamines as Efficient Ligands for Nickel-Catalyzed Enantioselective Michael Addition to Nitroalkenes. -Asymmetric Michael addition reaction of malonate (II) towards nitroolefins (I) proceeds with high yields and excellent enantioselectivities (92-99% e.e.) in the presence of a Ni-chiral tetrahydroisoquinoline-based diamine complex. -(WILCKENS, K.; DUHS, M.-A.; LENTZ, D.; CZEKELIUS*, C.; Eur. J. Org. Chem. 2011, 28, 5441-5446, http://dx.