Development of Axially Chiral Biazulenes for Catalysis

Abstract

Axially chiral biaryl ligands are ubiquitious in asymmetric transition metal-catalysed homogeneous catalysis. However, biazulene motifs have not previously been incorporated in the design of chiral ligands in asymmetric catalysis, despite the unique geometric and electronic properties of azulene derivatives. The aims of this project were to develop novel axially chiral biazulene-diphosphine, -diol and related species, encompassing the synthesis and resolution of their enantiomers, and to screen these compounds in the application towards common asymmetric reactions.The most significant achievement reached in this project was the synthesis andresolution of practicable quantities of an atropisomeric 1,1’-biazulene-2,2’-diolspecies (“1,1’-BazOL”), which has been employed in an asymmetric Ti-catalysedDiels–Alder reaction. Much progress has also been made towards the synthesis of other targets, like 1,1’-biazulene-2,2’-diphosphine (“1,1’-BazPhos”), 2,2’-biazulene-1,1’-diphosphine (“2,2’-BazPhos”) and 1,1’-biazulene-2,2’-phosphoric acid (“1,1’-BazPA”).

Date of Award	23 Nov 2016
Original language	English
Awarding Institution	University of Bath
Sponsors	Engineering and Physical Sciences Research Council
Supervisor	Simon Lewis (Supervisor)