The asymmetric inter- and intramolecular Heck and related reactions are comprehensively reviewed, from their original development to recent advances in terms of substrate scope, reactivity, regio- and enantioselectivity. Their reaction mechanisms/catalytic cycles are discussed in order to understand the concepts underpinning the significant recent developments of these processes. The design and application of new chiral ligands has been pivotal to reaction enhancements and, for each Heck and related process, we classify ligands by the nature of the denticity, chirality and donor atoms involved. In this manner, the continued development of ligand architectural design and application can be more easily monitored for each process. Significant improvements in reaction times, a disadvantage in many Heck reactions, have been addressed through a combination the use of microwave-assisted protocols and ligand design. The asymmetric Fujiwara-Moritani and oxidative boron Heck-type reactions, recent additions to Heck type processes, will also be discussed in this critical review (149 references).

Cent. Synth. Chem. Biol., Trinity Coll., Univ. Dublin, Dublin 2, Ire.; Eng.) -Lindner 04-230