The hydroacylation reaction allows for the 100% atom�efficient production of ketones from the combination of an alkene or alkyne with an aldehyde. The Achilles�heal of this potentially powerful transformation is the irreversible reductive decarbonylation from the acyl�hydride to give an inactive metal�carbonyl, which is promoted by a vacant site cis to an intermediate acyl. The initial best catalyst for this process was that developed by Bosnich, based upon [Rh(dppe)]+. We recently reported a development to these catalysts by the use of a hemilabile diphosphine ligand DPEphos, delivering catalyst systems capable of good levels of activity and catalyst robustness using �-S-substituted aldehydes in intermolecular reactions at loadings of 5-10 mol%. We now report new catalyst systems based upon small bite angle ligands, tBu2PCH2PtBu2. These catalysts can operate at only 0.1 mol% and offer a breakthrough in loadings, rate and substrate scope for the hydroacylation reaction.

Developing “3rd generation” hydroacylation catalysts that operate at only 0.1 mol%

243rd National Meeting (2012)

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