Ligand‐Enabled Chemo‐ and Regioselective Ir(I)‐Catalyzed Intermolecular Hydrocarbonation of Allenes: Access to Branched Products with All‐Carbon Quaternary Centers
Year: 2025
Type: article
Abstract: ppe can catalyze intermolecular hydrocarbonation reactions of allenes with precise control over the selectivity to yield highly valuable branched products instead of the more common linear derivatives. Using N-substituted 3-carboxamide pyrroles as C─H donors, the reaction gives exclusively C-4 substituted products, while furan analogues yield C-2 substituted derivatives. β-Unsubstituted acrylamides can also be used as C─H sources to give chiral skipped dienes. The additions are equally efficient using monosubstituted and 1,1-disubstituted allenes, enabling the efficient formation of products bearing tertiary and all-carbon quaternary stereocenters. Moreover, a preliminary analysis with chiral bisphosphinite ligands confirms the feasibility of an enantioselective variant. Computational (DFT) studies provide relevant insights into this remarkable ligand-driven branched selectivity.
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $5,510
Awards: G1091569419, G1175115578, G1369315627, G1496055848, G210041235, G2114305129, G2233490251, G2262748287, G2417469116, G2541661227, G2601397997, G300979063, G3092495004, G3300199665, G34346518, G3480869486, G3681454997, G3694284866, G3876637791, G4042783231, G4092263876, G410571670, G4228226468, G425668148, G451917667, G464105488, G5080475149, G5241663416, G5349246692, G5353516086, G5967599077, G6809441189, G6818627905, G7764612811, G7951387284, G8207841777, G901425231, G929308097
OpenAlex ID: W4413429317