New chiral diamide ligands containing redox-active hydroquinone groups. Synthesis and results in the palladium(II)-catalyzed 1,4-diacetoxylation of 1,3-dienes

Abstract

Chiral ligands 8– 11, 22 and 23 were synthesized from different chiral diamines as a new class of ligands for the Pd(II)-catalyzed 1,4-diacetoxylation of 1,3-dienes. The synthesis from the diamines and protected benzoic acids was performed in a few simple steps and gave the ligands in high overall yields. The hydroquinone groups present in the ligands are in situ oxidized to benzoquinone to give the active ligands. Application of these ligands in the 1,4-diacetoxylation reaction afforded the oxidation product with high regio- and diastereoselectivity and an enantiomeric excess up to 42% was obtained. Possible coordination modes of the metal to the ligand are discussed, and experiments were made to investigate the coordination by varying the reaction conditions or making changes to the ligands.