Decarboxylative Asymmetric Allylic Allylation DAAA

Trost was importantly able to extend this catalyst system to DAAA of acyclic enolate precursors to form a number of a-tertiary ketones using the same catalytic conditions [40]. More significant was the observation that the geometry of the enolate precursor affected both the rate of the reaction and the absolute configuration of the product suggesting that there is no significant geometric isomerisation of the enol carbonate or the Pd-enolate complex. 

The scope was found to be quite broad with sterically demanding substrates or those that contain a P-leaving group (no elimination) or other a-acidic functionality (no enolate scrambling). An a-fluorine atom could also be tolerated (Fig. 4.3). 

More recently Stoltz has described the application of an electron-deficient PHOX ligand, namely (5)-(CF3)3-t-BuPHOX (L3) in the DAAA of 

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