Lewis Acid Assisted Nickel-Catalyzed Cross-Coupling of Aryl Methyl Ethers by C−O Bond-Cleaving Alkylation: Prevention of Undesired β-Hydride Elimination

Liu, Xiangqian; Hsiao, Chien-Chi; Kalvet, Indrek; Leiendecker, Matthias; Guo, Lin; Schoenebeck, Franziska; Rueping, Magnus

Lewis Acid Assisted Nickel-Catalyzed Cross-Coupling of Aryl Methyl Ethers by C−O Bond-Cleaving Alkylation: Prevention of Undesired β-Hydride Elimination

Type

Article

Authors

Liu, Xiangqian
Hsiao, Chien-Chi
Kalvet, Indrek
Leiendecker, Matthias
Guo, Lin
Schoenebeck, Franziska
Rueping, Magnus

KAUST Department

Chemical Science Program
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division

Online Publication Date

2016-04-08

Print Publication Date

2016-05-10

Date

2016-04-08

Abstract

In the presence of trialkylaluminum reagents, diverse aryl methyl ethers can be transformed into valuable products by C-O bond-cleaving alkylation, for the first time without the limiting β-hydride elimination. This new nickel-catalyzed dealkoxylative alkylation method enables powerful orthogonal synthetic strategies for the transformation of a variety of naturally occurring and easily accessible anisole derivatives. The directing and/or activating properties of aromatic methoxy groups are utilized first, before they are replaced by alkyl chains in a subsequent coupling process.

Citation

Liu X, Hsiao C-C, Kalvet I, Leiendecker M, Guo L, et al. (2016) Lewis Acid Assisted Nickel-Catalyzed Cross-Coupling of Aryl Methyl Ethers by C−O Bond-Cleaving Alkylation: Prevention of Undesired β-Hydride Elimination. Angewandte Chemie International Edition 55: 6093–6098. Available: http://dx.doi.org/10.1002/anie.201510497.

Acknowledgements

X.L. and L.G. were supported by the China Scholarship Council, C.-C.H. was supported by a DAAD fellowship, and M.L. was supported by a Kekule fellowship (Fonds der Chemischen Industrie) and the Studienstiftung des deutschen Volkes. We gratefully acknowledge the computing time granted on the RWTH Bull Cluster in Aachen (JARA0091).