Palladium-catalyzed asymmetric prenylation of oxindoles to selectively afford either the prenyl or the reverse prenyl product has been demonstrated. Control of regioselectivity in this transformation is governed by choice of ligand, solvent, and halide additive. The resulting prenylated and reverse prenylated products have been transformed into ent-flustramides and ent-flustramines A and B. Additionally, control in regio- and diastereoselectivity has been obtained using π-geranylpalladium complexes.

Glycogen synthase kinase-3 (GSK3) is involved in signaling from the insulin receptor. Inhibitors of GSK3 are expected to effect lowering of plasma glucose similar to insulin, making GSK3 an attractive target for the treatment of type 2 diabetes. Herein we report the discovery of a series of potent and selective GSK3 inhibitors. Compounds 7-12 show oral activity in an in vivo model of type II diabetes, and 9 and 12 have desirable PK properties.

The use of a bifunctional nitrogen nucleophile and an allyl carbonate starting material in successive enantioselective palladium- and diastereoselective rhodium-catalyzed reactions enables the rapid assembly of unique amino aziridine products. Further elaboration of these materials affords complex, stereodefined polyamine architectures, thus demonstrating the power of these combined methods for simplifying asymmetric C−N bond construction.

A novel synthetic strategy towards the asymmetric synthesis of vicinal diols bearing a tertiary center is presented. The method encompasses the dinuclear Mg-catalyzed asymmetric addition of ethyl diazoacetate into several aldehydes, oxidation of the diazo functionality, and diastereoselective alkyl transfer of various organometallics into the resulting chiral β-hydroxy-α-ketoesters to afford a diverse range of 1,2-diols in high yield, diastereoselectivity, and chirality transfer.

Magnesium-catalyzed enantioselective aldol between ethyl diazoacetate and aromatic, aliphatic, and α,β-unsaturated aldehydes affords α-diazo-β-hydroxy-esters in high enantioselectivities. Aldol adducts resulting from this asymmetric transformation are versatile intermediates towards the synthesis of several ester containing chiral building blocks.