Two Stereoinduction Events in One C-H Activation Step: A Route towards Terphenyl Ligands with Two Atropisomeric Axes.

Abstract

Herein we disclose the synthesis of original chiral scaffolds-ortho-orientated terphenyls presenting two atropisomeric Ar-Ar axes. These unusual structures were built up by using the C-H activation approach, and remarkably, both chiral axes were controlled with excellent stereoselectivity in a single transformation. During the reaction, not only does atroposelective functionalization of a biaryl precursor occur to establish one stereogenic axis, but an unprecedented atropo-stereoselective C-H arylation also takes place to generate the second stereogenic element. These enantiomerically pure ortho-terphenyls show an original tridimensional structure and thus constitute a unique foundation for building up a library of enantiomerically pure bidentate ligands, such as the new ligands S/N-Biax and diphosphine BiaxPhos.