Abstract
The Heck reaction is a widely used carbon–carbon bond forming process in organic synthesis. A prominent variant that has found widespread application in targeted complex‐molecule synthesis is the asymmetric intramolecular Heck reaction. This methodology has outshone another powerful facet of Heck chemistry that has been prospering in recent years, namely heteroatom‐directed Heck reactions. Initially designed to achieve high regiocontrol in intermolecular reactions, this technique has recently been successfully applied to highly diastereoselective and even enantioselective substrate‐directed inter‐ as well as intramolecular Heck reactions. This microreview delineates, for the first time, the evolution of this chemistry from regio‐ to diastereo‐ and, finally, enantioselective transformations. Flexible syntheses ofstereodefined, multi‐arylated alkenes, the diastereoselective construction of tertiary and quaternary carbon centres, as well as combining substrate‐ with catalyst‐control in anenantioselective transformation are covered. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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