Synthesis of New Camphor-Based Carbene Ligands and Their Application in a Copper-Catalyzed Michael Addition with B₂Pin₂

Abstract

In this work the synthesis of new asymmetric camphor-based 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 copper-catalyzed B₂Pin₂ [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.

Key words

N-heterocyclic carbenes - copper - catalysis - Michael addition - camphor

• References

• 1 Current address: COMSATS Institute of Information Technology, Defence Road, Off Raiwind Road, Lahore, Pakistan.
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