Working Paper
Authors
- Jordan De Jesus Silva
ETH Zurich ,
- Niccolò Bartalucci ETH Zurich ,
- Benson Jelier ETH Zurich ,
- Samantha Grosslight University of Utah ,
- Tobias Gensch University of Utah & Technical University of Berlin ,
- Claas Schünemann Leibniz Institute for Catalysis ,
- Bernd Müller Leibniz Institute for Catalysis ,
- Paul C. J. Kamer Leibniz Institute for Catalysis ,
- Christophe Copéret ETH Zurich ,
- Matthew S. Sigman University of Utah ,
- Antonio Togni ETH Zurich
Abstract
A synthetic method for the palladium-catalyzed cyanation of aryl boronic acids using bench stable and non-toxic N-cyanosuccinimide has been developed. High-throughput experimentation facilitated the screen of 90 different ligands and the resultant statistical data analysis identified that ligand σ–donation, π–acidity and sterics are key drivers that govern yield. Categorization into three ligand groups – monophosphines, bisphosphines and miscellaneous – was performed before the analysis. For the monophosphines, the yield of the reaction increases for strong σ–donating, weak π–accepting ligands, with flexible pendant substituents. For the bisphosphines, the yield predominantly correlates with ligand lability. The applicability of the designed reaction to a wider substrate scope was investigated, showing good functional group tolerance in particular with boronic acids bearing electron-withdrawing substituents. This work outlines the develop-ment of a novel reaction, coupled with a fast and efficient workflow to gain understanding of the optimal ligand properties for the design of improved palladium cross-coupling catalysts.
Content

Supplementary material

Supplementary Information
Contains details on the reagents and setups used, catalytic data, NMR spectra and modelling details.