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

• Published in: Journal of the American Chemical Society Vol. 127; no. 26; pp. 9603 - 9611
• Main Authors: Peng, Hai-Yan, Lam, Chi-Keung, Mak, Thomas C. W, Cai, Zongwei, Ma, Wai-Tang, Li, Yu-Xue, Wong, Henry N. C
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 06.07.2005; Amer Chemical Soc
• Subjects: Catalysis; Catalytic reactions; Chemistry; Chemistry, Multidisciplinary; Condensed matter: structure, mechanical and thermal properties; Coordination compounds; Exact sciences and technology; General and physical chemistry; Inorganic chemistry and origins of life; Inorganic compounds; Metal complexes; Physical Sciences; Physics; Preparations and properties; Science & Technology; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; CYCLIC NANOSTRUCTURES; CLATHRATE INCLUSION COMPOUND; RHODIUM; ABSOLUTE-CONFIGURATION; CRYSTAL-STRUCTURE; MOLECULAR ARCHITECTURE; RESOLUTION; TETRAPHENYLENES; CHEMISTRY; COORDINATION; Pentacyclic compound; Molecular packing; Platinum Complexes; Catalytic reaction; Molecular structure; Organic ligand; Inorganic synthesis; Transition metal Complexes; X ray diffraction; Hydrogenation; Asymmetric reaction; Aromatic compound; Catalyst activity; Crystalline structure
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja051013l

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.