Palladium-Catalysed Decarboxylative Asymmetric Protonation DAP

A key extension of the DAAA was realised by Stoltz and co-workers in 2006 with their seminal report on a stereoablative enantioconvergent decarboxylative asymmetric protonation [51]. This was realised by intercepting the intermediate (103) 

The optimised conditions were then applied to a range of cyclic a-alkyl and a-benzyl substituted P-keto allyl esters to generate the corresponding a-tertiary ketones in good yields and excellent enantioselectivities. Interestingly the fused aromatic substrates such as tetralone 102 gave the opposite sense of stereoinduction in the resulting tertiary product (105), compared to the monocyclic compounds such 

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