Consecutive chirality transfer: efficient synthesis of chiral C,O-chelated BINOL/gold(iii) complexes for asymmetric catalysis and chiral resolution of disubstituted BINOLs

Abstract

A novel approach for efficient synthesis of chiral C,O-chelated BINOL/gold(III) complexes by diastereomeric resolution using enantiopure BINOL as a chiral resolving agent was demonstrated. The BINOL/gold(III) diastereomers with different solubility were separated by simple filtration, providing optically pure BINOL/gold(III) complexes with up to >99 : 1 dr. By combining this with an efficient BINOL ligand dissociation process, a simple and column-free method for chiral resolution of racemic gold(III) dichloride complexes on a gram scale was established, affording their enantiopure forms in good yields. Conversely, the resolved enantiopure gold(III) dichloride complexes could serve as chiral resolving agents to resolve disubstituted BINOL derivatives, achieving both BINOLs and gold(III) complexes in good to excellent yields (overall 77–96% and 76–95%, respectively) with a high optical purity of up to 99% ee. Through a consecutive chirality transfer process, the chiral information from an inexpensive chiral source was transferred to highly valuable gold(III) complexes, followed by sterically bulky BINOL derivatives. This work would open a new synthetic strategy facilitating the development of structurally diverse chiral gold(III) complexes and gold(III)-mediated chiral resolution of BINOL derivatives. In addition, this new class of C,O-chelated BINOL/gold(III) complexes achieved asymmetric carboalkoxylation of ortho-alkynylbenzaldehydes with an excellent enantioselectivity of up to 99% ee.