A Dual Palladium and Copper Hydride Catalyzed Approach for Alkyl–Aryl Cross-Coupling of Aryl Halides and Olefins

Angewandte Chemie - International Edition

5 years ago

A Dual Palladium and Copper Hydride Catalyzed Approach for Alkyl–Aryl Cross-Coupling of Aryl Halides and Olefins

Stephen L. Buchwald, Lauren N. Dupuis, Michael T. Pirnot, Stig D. Friis

We report an efficient means of sp2–sp3 cross coupling for a variety of terminal monosubstituted olefins with aryl electrophiles using Pd and CuH catalysis. In addition to its applicability to a range of aryl bromide substrates, this process was also suitable for electron-deficient aryl chlorides, furnishing higher yields than the corresponding aryl bromides in these cases. The optimized protocol does not require the use of a glovebox and employs air-stable Cu and Pd complexes as precatalysts. A reaction on 10 mmol scale further highlighted the practical utility of this protocol. Employing a similar protocol, a series of cyclic alkenes were also examined. Cyclopentene was shown to undergo efficient coupling under these conditions. Lastly, deuterium-labeling studies indicate that deuterium scrambling does not take place in this sp2-sp3 cross coupling, implying that β-hydride elimination is not a significant process in this transformation. Cross-coupling: A protocol for sp2–sp3 cross-coupling of terminal alkenes and aryl halides is reported. A broad substrate scope based on air-stable precatalysts is detailed. This reaction is shown on a 10 mmol scale, along with preliminary studies with cyclic alkenes that highlight cyclopentene as an effective coupling partner.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201703400