Enantioselective Allylation from Allene, a Petroleum Cracking Byproduct

<p>Allene (C3H4) gas is produced and separated on million-metric-ton scale per year during petroleum refining but is only rarely employed in chemical manufacturing. Meanwhile, the addition of an allyl group (C3H5) to ketone-containing molecules is among the most common</p> <p>and prototypical reactions in organic synthesis. Herein, we report that the combination of allene with environmentally benign hydrosilanes can replace harsher, more wasteful, and more</p> <p>expensive allylmetal reagents in enantioselective ketone allylation reactions. This process is catalyzed by an earth-abundant metal and commercially available ligands, operates without specialized equipment or pressurization, and tolerates a broad range of functional groups. Furthermore, the exceptional chemoselectivity of our catalyst system enables industrially relevant C3 hydrocarbon mixtures of allene with methylacetylene and propylene to be applied</p> <p>directly. Based on our strategy, we anticipate the rapid development of methods that leverage this unexploited feedstock as a surrogate for existing nucleophilic allylation reagents.</p>