The first asymmetric total synthesis of the unnatural enantiomer of cytotoxic awajanomycin (1) is reported. The synthetic approach features first a convergent strategy using the cross-olefin metathesis reaction to link the lipid side chain 2 and the piperidinone core structure 3. The second feature of the synthesis resides on the construction of segment 3 from the building block 5 via a three-component tandem reaction on the mixed imide 12. Through this work, the stereochemistry at C-11 and the absolute configuration of awajanomycin were established as 3R,5R,6S,8S,11S.

A highly efficient one-pot process via a tandem reaction of catalytic asymmetric hydrogenation and oxa-Michael cyclization for the synthesis of 2,6-cis-disubstituted tetrahydropyrans has been developed (ee up to 99.9%, cis/trans-selectivity up to 99:1). This method provides a concise route to (-)-centrolobine (68.8% yield, three steps).

Ruthenium-catalyzed highly selective codimerization of N-acetyl α-arylenamines with ethyl acrylates is reported. This codimerization reaction provides a new efficient method for the synthesis of α,β-unsaturated γ-amino esters with a quaternary center.

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