Chapter 1 gives the reader a background on cross-coupling reactions, in particular palladium mediated couplings. Furthermore the importance of ligands, including phosphines and N-heterocyclic carbenes (NHC), in such cross-coupling reactions is explored. Chapter 2 provides a background to the reductive lithiation of phosphines, followed by an account of our investigation of BINAP functionalisati...

In model studies towards the quaternary centre at the heart of diazonamide A (early structure 2; revised structure 1), cyclisations of the alkene-substituted iodoaryls 4, 13, 18 and 23, under Heck reaction conditions, were shown to lead to the corresponding benzodihydrofuran 5, benzofuranone 14 and the oxindoles 19 and 24 respectively, in 50-80% yield. Further manipulation of the benzodihydrofu...

The asymmetric synthesis of L-699,392, a leukotriene antagonist, is reported. The main framework of the molecule is formed via a Heck reaction. The introduction of the asymmetric center was accomplished by the chiral reduction of prochiral ketone using B-chlorodiisopinocampheylborane. A very high asymmetric amplification was observed in which 95% ee product can be obtained from 70% optically pu...

A number of novel benzimidazolium salts having aryl substituents such as N-phenyl, 4-chlorophenyl and various alkyl substituents were synthesized. Their microwave-assisted catalytic activities were evaluated in Heck-Mizoroki and Suzuki-Miyaura cross-coupling reactions using a catalytic system consisting of Pd(OAc)(2)/K(2)CO(3) in DMF/H(2)O under mild reaction conditions with consistent high y...

Pd-catalyzed aerobic oxidative coupling of vinylboronic acids and electronically unbiased alkyl olefins provides regioselective access to 1,3-disubstituted conjugated dienes. Catalyst-controlled regioselectivity is achieved by using 2,9-dimethylphenanthroline as a ligand. The observed regioselectivity is opposite to that observed from a traditional (nonoxidative) Heck reaction between a vinyl b...