Helical Bisphosphinites in Asymmetric Tsuji-Trost Allylation: a Remarkable P:Pd Ratio Effect

This article discloses a study on a chiral bis-phosphorylated-helical ligand in the palladium-catalyzed Tsuji-Trost allylation. The use of 2,15-bisphosphinite-[6]-helicenes revealed a remarkable ligand effect, in which the (R) and (S) isomeric products can be selectively formed as a direct function of the amount of ligand introduced. Investigation of the organometallic species involved through P-31 NMR spectroscopic analysis of a model complex and X-Ray diffraction analysis together with DFT calculations shed light on this phenomenon.

Automated summary

This study reveals the significant role of a chiral bis-phosphorylated-helical ligand in the palladium-catalyzed Tsuji-Trost allylation. It was found that the (R) and (S) isomeric products can be selectively formed based on the amount of ligand introduced. Analysis through P-31 NMR spectroscopy, X-Ray diffraction, and DFT calculations shed light on the mechanism behind the role of organometallic species involved.