Stereoselectivity of Metal-Catalyzed Cyclizations of 1,6-Dienes

In this article, the stereoselectivity of metal-catalyzed cyclizations of 1,6-dienes is examined according to the elementary steps which can be envisaged as triggers of the rearrangements. Crucial results have been obtained which demonstrate that enantio­selective and diastereoselective cyclizations are possible. However, a lack of stereoselectivity is often observed for 1,6-dienes having a prochiral tether, which appears to originate in the lack of differentiation between the two olefins of the substrates. 1 Introduction 2 Oxidative Cyclometalation 3 Copper-Catalyzed Photocycloaddition 4 Intermolecular Hydrometalation 5 Carbometalation and Sila-Metalation 6 π-Allyl Formation in Metallo-Ene Cyclization 7 Olefin Electrophilic Activation 8 C–H Activation 9 Conclusion