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Enantioselective Allylation from Allene, a Petroleum Cracking Byproduct

preprint
submitted on 10.11.2018 and posted on 13.11.2018 by Richard Y. Liu, Yujing Zhou, Yang Yang, Stephen L. Buchwald

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

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

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

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.

Funding

GM58160

GM122483

GM58160-17S1

History

Email Address of Submitting Author

yjzhou@mit.edu

Institution

MIT

Country

United States

ORCID For Submitting Author

0000-0002-8161-8560

Declaration of Conflict of Interest

No conflict of interest

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