Affiliation:
1. Shanghai Key Laboratory of Green Chemistry and Chemical Processes State Key Laboratory of Petroleum Molecular & Process Engineering School of Chemistry and Molecular Engineering East China Normal University Shanghai 200062 China
2. Shanghai Frontiers Science Center of Molecule Intelligent Syntheses School of Chemistry and Molecular Engineering East China Normal University Shanghai 200062 China
Abstract
AbstractPd‐catalyzed alkoxycarbonylation of internal alkynes provides a straightforward access to α,β‐disubstituted acrylic esters. Compared with the well‐established regioselective alkoxycarbonylation of terminal alkynes, the regioselective hydrocarboxylation of non‐functionalized unsymmetric internal alkynes was more challenging owing to the delicate differences of properties between the two substituents. Herein, by using either monophosphine ligand based on 2,3‐dihydrobenzo[d][1,3]oxaphosphole motif or bidentate ligand Ph‐Phox, the regioselective alkoxycarbonylations of aryl‐aryl, aryl‐alkyl and alkyl‐alkyl disubstituted alkynes were achieved, giving a diversity of trisubstituted α,β‐unsaturated carboxylic esters with moderate to excellent yields and high regioselectivity. The synthetic utility of obtained α,β‐disubstituted acrylic esters was demonstrated.
Funder
National Natural Science Foundation of China