AbstractDehydroabietic acid (DAA) promotes palladium(0)-catalysed cyclisations of arene-tethered 1,7-enynols and 1,m-enynoates (m=6,7) to give fused carbocyclic dienes. 6,6,6,5-Tetracyclic lactones are accessible by one-pot cycloisomerisation/Diels–Alder reaction/lactonisation from 1,7-enynols. Furthermore, asymmetric counteranion-directed catalysis has been developed, which afforded an indene derivative with an all-carbon quaternary stereogenic center.

t-BuOK-mediated rearrangement of 1,3-ketoesters with 2-(azidomethyl) aromatics in a two-step, one-pot telescoped sequence affords β-enaminoketoesters in moderate to good yields. A novel pathway is proposed in which the umpolung of the azide is achieved from electrophilicity to nucleophilicity via deprotonation and undergoes nucleophilic attack onto the 1,3-ketoester.

A highly enantioselective rhodium catalysed asymmetric arylation (RCAA) of nitroolefins with arylboronic acids is presented using a newly developed, C1-symmetric, non-covalent interacted, phellandrene derived, nordehydroabietyl amide-containing chiral diene under mild conditions. Stereoelectronic effects were studied, suggesting an activation of the bound substrate through the secondary amide as a hydrogen-bond donor.