Stereoselective synthesis of hydroxylated 3-aminoazepanes using a multi-bond forming, three-step tandem process.

A multi-bond forming, three-step tandem process involving a palladium(II)-catalysed Overman rearrangement and a ring closing metathesis reaction has been utilised for the efficient synthesis of a 2,3,6,7-tetrahydro-3-amidoazepine. Substrate directed epoxidation or dihydroxylation of this synthetic intermediate has allowed the diastereoselective synthesis of hydroxylated 3-aminoazepanes including the syn-diastereomer of the balanol core. Asymmetric synthesis of the 2,3,6,7-tetrahydro-3-amidoazepine motif was also achieved using a chiral palladium(II)-catalyst during the Overman rearrangement.