Enantioselective silicon–boron additions to cyclic 1,3-dienes catalyzed by the platinum group metal complexes

Silaborations of 1,3-cyclohexadiene and 1,3-cycloheptadiene were achieved using catalysts prepared from different combinations of phosphorus ligands and group 10 metal compounds. For the six-membered compound, 1,4-adducts with up to 82% ee were obtained employing Pt(0) and phosphoramidite ligands. For the seven-membered diene optimal conditions were found using catalysts based on Ni(0), but the highest selectivity observed was merely 22% ee. No improvement of the chiral induction was obtained using chiral silylboranes in combination with chiral phosphoramidite ligands in the additions to 1,3-cyclohexadiene. The adduct obtained from cyclohexadiene was used in allylborations of aldehydes under microwave irradiation to produce homoallylic alcohols with moderate to good diastereoselectivity.

Graphical abstractEnantioselective 1,4-silaborations of 1,3-cyclohexadiene and 1,3-cycloheptadiene were achieved using chiral catalysts. For 1,3-cyclohexadiene up to 82% ee was observed. The resulting 1,4-adduct was successfully used in microwave assisted allylboration reactions that proceeded with good to moderate diastereoselectivity.Figure optionsDownload full-size imageDownload as PowerPoint slide