Rhodium-catalysed hydroboration employing new Quinazolinap ligands; an investigation into electronic effects

As part of an ongoing effort to improve the efficiency and substrate scope of our Quinazolinap ligand series in the rhodium-catalysed asymmetric hydroboration of vinyl arenes, 2-(p-trifluoromethylphenyl)Quinazolinap and 2-(p-methoxyphenyl)-Quinazolinap have been synthesised and resolved in good yield. These, along with the previously reported 2-(2-pyridyl)-Quinazolinap and 2-(2-pyrazinyl)-Quinazolinap, form part of an electronic series of Quinazolinap ligands synthesised in order to explore electronic effects in this ligand class. The application of this series of ligands to the rhodium-catalysed asymmetric hydroboration of a range of vinylarenes is described. Good conversions and regioselectivities as well as excellent enantioselectivities up to 97% were obtained. 2-(p-Methoxyphenyl)-Quinazolinap demonstrated consistently high enantioselectivities in the hydroboration of sterically demanding vinylarenes. (C) 2010 Elsevier Ltd. All rights reserved.