Preparation of chiral EC(sp3)E’ phosphine-based mono- and di-nuclear palladium pincer complexes

• Main Author: Tay, Wee Shan
• Other Authors: Leung Pak Hing
• Format: Theses and Dissertations
• Language: English
• Published: 2016
• Subjects: DRNTU::Science::Chemistry::Organic chemistry::Organometallic compounds
• Online Access: http://hdl.handle.net/10356/67020
• Institution: Nanyang Technological University

Ten enantiopure Pd pincer complexes with aliphatic and unsymmetrical characteristics have been synthesized efficiently. Chirality on the ligand backbone was introduced via an asymmetric H-P bond addition reaction by two structurally-dissimilar catalysts with >99% ee’s. Challenging C(sp3)-H bond activation during palladation proceeded with high yields and excellent diastereoselectivities under optimized conditions. Several crystal structures were isolated and discussed. Selected pincer complexes were also employed in a chirality “self-breeding” protocol, in which infinite replicates of a catalyst may be synthesized by itself. Excellent results were obtained, with the selected complex being capable of producing itself with the exact absolute stereoconfiguration with >99% ee at RT.