Chiral Rodlike Platinum Complexes, Double Helical Chains, and Potential Asymmetric Hydrogenation Ligand Based on “Linear” Building Blocks: 1,8,9,16-Tetrahydroxytetraphenylene and 1,8,9,16-Tetrakis(diphenylphosphino)tetraphenylene

This paper is concerned with the synthesis of 1,8,9,16-tetrahydroxytetraphenylene (3a) via copper(II)-mediated oxidative coupling, its resolution to optical antipodes, and its conversion to 1,8,9,16-tetrakis(diphenylphosphino)tetraphenylene (3b). On the basis of these chiral “linear” building blocks, three rodlike
chiral complexes, triblock (R,R,R,R)-17 and (S,S,S,S)-20 and pentablock (R,R,R,R,R,R,R,R)-22, were
constructed. As a hydrogen bond donor, racemic and optically active 3a was allowed to assemble with
linear acceptors to afford highly ordered structures. A 1:1 adduct of 4,4‘-bipyridyl and (±)-3a exists in a
dimeric form of 3a linked by 4,4‘-bipyridyl through hydrogen bonds. Pyrazine serves as a short linker between
achiral parallel chains each formed by (±)-3a, while self-assembly of homochiral 3a into alternate parallel
chains occurs in the adduct of 5,5‘-dipyrimidine with (±)-3a. Self-assembly of (S,S)-3a or (R,R)-3a with
4,4‘-dipyridyl yielded a packing of chiral double helical chains formed by chiral tetrol 3a molecules. A novel
chiral ligand, (S,S)-23, derived from 3a was used in the asymmetric catalytic hydrogenation of α-acetamidocinnamate, yielding up to 99.0% ee and 100% conversion.