title: [3+3] Cyclocondensation of Disubstituted Biphenyl Dialdehydes: Access to Inherently Luminescent and Optically Active Hexa-substituted C3-Symmetric and Asymmetric Trianglimine Macrocycles.
abstract: A general synthetic route to inherently luminescent and optically active 6-fold substituted C3-symmetric and asymmetric biphenyl-based trianglimines has been developed. The synthesis of these hexa-substituted triangular macrocycles takes advantage of a convenient method for the synthesis of symmetrically and asymmetrically difunctionalized biphenyl dialdehydes through a convergent two-step aromatic nucleophilic substitution-one-pot Suzuki-coupling reaction protocol. A modular [3+3] diamine-dialdehyde cyclocondensation reaction between both the symmetrically and asymmetrically difunctionalized-4,4'-biphenyldialdehydes with enantiomerically pure (1R,2R)-1,2-diaminocyclohexane was employed to construct the hexa-substituted triangular macrocycles. B97-D/6-311G(2d,p) density functional theory determined structures and X-ray crystallographic analysis reveal that the six substituents appended to the biphenyl legs of the trianglimine macrocycles adopt an alternating conformation not unlike the 1,3,5-alternate conformation observed for calix[6]arenes. Reduction of the imine bonds using NaBH4afforded the corresponding 6-fold substituted trianglamine without the need to alkylate the amine nitrogen atoms which could hinder their later use as metal coordination sites and without having to introduce asymmetric carbons.
authors.affiliation: Institute for Molecular Design and Synthesis, School of Pharmaceutical Science and Technology, Tianjin University , 92 Weijin Road, Nankai District, Tianjin 300072, P. R. China.
authors.forename: Zhenzhen
authors.initials: Z
authors.lastname: Wang
authors.affiliation: Institute for Molecular Design and Synthesis, School of Pharmaceutical Science and Technology, Tianjin University , 92 Weijin Road, Nankai District, Tianjin 300072, P. R. China.|Chemical Industries Research Division, Department of Photochemistry, National Research Centre , 33 El Buhouth Street, Giza 12622, Egypt.
authors.forename: Hany F
authors.initials: HF
authors.lastname: Nour
authors.affiliation: Institute for Molecular Design and Synthesis, School of Pharmaceutical Science and Technology, Tianjin University , 92 Weijin Road, Nankai District, Tianjin 300072, P. R. China.|Department of Chemistry, University of Zürich , Winterthurerstrasse 190, 8057 Zürich, Switzerland.
authors.forename: Loïc M
authors.initials: LM
authors.lastname: Roch
authors.affiliation: Institute for Molecular Design and Synthesis, School of Pharmaceutical Science and Technology, Tianjin University , 92 Weijin Road, Nankai District, Tianjin 300072, P. R. China.
authors.forename: Minjie
authors.initials: M
authors.lastname: Guo
authors.affiliation: Institute for Molecular Design and Synthesis, School of Pharmaceutical Science and Technology, Tianjin University , 92 Weijin Road, Nankai District, Tianjin 300072, P. R. China.
authors.forename: Wenjiao
authors.initials: W
authors.lastname: Li
authors.affiliation: Institute for Molecular Design and Synthesis, School of Pharmaceutical Science and Technology, Tianjin University , 92 Weijin Road, Nankai District, Tianjin 300072, P. R. China.
authors.forename: Kim K
authors.identifier: 0000-0001-7171-3487
authors.initials: KK
authors.lastname: Baldridge
authors.affiliation: Institute for Molecular Design and Synthesis, School of Pharmaceutical Science and Technology, Tianjin University , 92 Weijin Road, Nankai District, Tianjin 300072, P. R. China.
authors.forename: Andrew C H
authors.initials: AC
authors.lastname: Sue
authors.affiliation: Institute for Molecular Design and Synthesis, School of Pharmaceutical Science and Technology, Tianjin University , 92 Weijin Road, Nankai District, Tianjin 300072, P. R. China.
authors.forename: Mark A
authors.identifier: 0000-0003-0398-5063
authors.initials: MA
authors.lastname: Olson