In this work the synthesis of new asymmetric diamine ligands from camphoric acid is described. The new diamines can be directly prepared in a regioselective arylation of the less hindered primary amine group of (+)-cis-1,2,2-trimethylcyclopentane-1,3-diamine via a Buchwald-Hartwig amination in high yields. The resulting diamines incorporate a secondary and primary amine group and were successfully applied as ligands in a copper-catalyzed Henry reaction.

In this work the synthesis of new asymmetric camphorbased carbene ligands from camphoric acid is described. The new carbenes can be prepared directly in high yields by the sequence: regioselective arylation of the less hindered primary amine group of (+)-cis-1,2,2-trimethylcyclopentane-1,3-diamine by Buchwald-Hartwig amination, treatment with trimethyl orthoformate, and finally treatment with a benzylic halide. The resulting carbenes, incorporating an aryl and a benzylic substituent, were successfully applied as ligands in a coppercatalyzed B 2 Pin 2 [bis(pinacolato)diboron] addition to an unsaturated carbonyl compound. Depending on the substituents dual stereocontrol was observed and one enantiomer was obtained in up to 82% ee and the opposite enantiomer in up to 78% ee.

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