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This report describes the synthesis of a [2.2]paracyclophane‐derived annulated 3‐amino‐imidazole ligand library through a Groebke‐Blackburn‐Bienaymé three‐component reaction (GBB‐3CR) approach employing formyl‐cyclophanes in combination with diverse aliphatic and aromatic isocyanides and heteroaromatic amidines. The GBB‐3CR process gives access to skeletally‐diverse cyclophanyl imidazole ligands, namely 3‐amino‐imidazo[1,2‐a]pyridines and imidazo[1,2‐a]pyrazines. Additionally, a one‐pot protocol for the GBB‐3CR by an in situ generation of cyclophanyl isocyanide is demonstrated. The products were analyzed by detailed spectroscopic techniques, and the cyclophanyl imidazo[1,2‐a]pyridine was confirmed unambiguously by single‐crystal X‐Ray crystallography. The cyclophanyl imidazole ligands can be readily transformed to showcase their useful utility in preparing N,C‐palladacycles through regioselective ortho‐palladation. [ABSTRACT FROM AUTHOR]

Fused-imidazoles, Groebke-Blackburn-Bienaymé (GBB) reaction, Isocyanide Chemistry, Multicomponent reactions, [2.2]Paracyclophane Cover Feature: Diversity-Oriented Synthesis of [2.2]Paracyclophane-derived Fused Imidazo[1,2-a]heterocycles by Groebke-Blackburn-Bienaymé Reaction: Accessing Cyclophanyl Imidazole Ligands Library (Chem. Eur. J. 3/2022) Keywords: Fused-imidazoles; Groebke-Blackburn-Bienaymé (GBB) reaction; Isocyanide Chemistry; Multicomponent reactions; [2.2]Paracyclophane EN Fused-imidazoles Groebke-Blackburn-Bienaymé (GBB) reaction Isocyanide Chemistry Multicomponent reactions [2.2]Paracyclophane 1 1 1 01/18/22 20220113 NES 220113 B The Groebke-Blackburn-Bienaymé three-component reaction b (GBB-3CR) has contributed enormously to the progress of organic synthesis, medicinal chemistry, and materials science. [Extracted from the article]

This report describes the synthesis of a [2.2]paracyclophane‐derived annulated 3‐amino‐imidazole ligand library through a Groebke‐Blackburn‐Bienaymé three‐component reaction (GBB‐3CR) approach employing formyl‐cyclophanes in combination with diverse aliphatic and aromatic isocyanides and heteroaromatic amidines. The GBB‐3CR process gives access to skeletally‐diverse cyclophanyl imidazole ligands, namely 3‐amino‐imidazo[1,2‐a]pyridines and imidazo[1,2‐a]pyrazines. Additionally, a one‐pot protocol for the GBB‐3CR by an in situ generation of cyclophanyl isocyanide is demonstrated. The products were analyzed by detailed spectroscopic techniques, and the cyclophanyl imidazo[1,2‐a]pyridine was confirmed unambiguously by single‐crystal X‐Ray crystallography. The cyclophanyl imidazole ligands can be readily transformed to showcase their useful utility in preparing N,C‐palladacycles through regioselective ortho‐palladation. [ABSTRACT FROM AUTHOR]

This report describes the synthesis of a [2.2]paracyclophane-derived annulated 3-amino-imidazole ligand library through a Groebke-Blackburn-Bienaymé three-component reaction (GBB-3CR) approach employing formyl-cyclophanes in combination with diverse aliphatic and aromatic isocyanides and heteroaromatic amidines. The GBB-3CR process gives access to skeletally-diverse cyclophanyl imidazole ligands, namely 3-amino-imidazo[1,2-a]pyridines and imidazo[1,2-a]pyrazines. Additionally, a one-pot protocol for the GBB-3CR by an in situ generation of cyclophanyl isocyanide is demonstrated. The products were analyzed by detailed spectroscopic techniques, and the cyclophanyl imidazo[1,2-a]pyridine was confirmed unambiguously by single-crystal X-Ray crystallography. The cyclophanyl imidazole ligands can be readily transformed to showcase their useful utility in preparing N,C-palladacycles through regioselective ortho-palladation., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The modular synthesis of Au(I)/Ru(II) decorated mono- and heterobimetallic complexes with π-conjugated [2.2]paracyclophane is described. [2.2]Paracyclophane serves as a rigid spacer which holds the metal centers in precise spatial orientations and allows metal-to-metal distance modulation. A broad set of architectural arrangements of pseudo -geminal, -ortho, -meta, and -para substitution patterns were employed. Metal-to-metal distance modulation of Au(I)/Ru(II) heterobimetallic complexes and the innate transannular π-communication of the cyclophanyl scaffold provides a promising platform for the investigations of structure-activity relationship and cooperative effects. The Au(I)/Ru(II) heterobimetallic cyclophanyl complexes are stable, easily accessible, and exhibit promising catalytic activity in the visible-light promoted arylative Meyer-Schuster rearrangement., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Late-stage modification is highly desirable for the diversification and modification of biologically active compounds. Peripheral editing (e.g., C-H activation) has been the predominant methodology, whereas skeletal editing is in its infancy. The single-atom N-deletion using anomeric amide reagents constitutes a powerful tool to modify the underlying molecular skeletons of secondary amines. N-pivaloyloxy-N-alkoxyamide is easily prepared on a large scale and promotes C-C bond formation in good yields under the extrusion of N 2 for a variety of (cyclic) aliphatic amines. The exploitation of widely available amines allows the use of existing amine synthesis protocols to translate into the construction of new C-C bonds, enabling ring contraction and the potential for structure optimization of biologically active compounds., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Selective activation/functionalization of C-H bonds has emerged as an atom- and step-economical process at the forefront of modern synthetic chemistry. This work reports palladium-catalyzed exclusively para-selective C-H activation/aryl-aryl bond formation with a preference over N-arylation under the Buchwald-Hartwig amination reaction of 4-phenylamino[2.2]paracyclophane. This innovative synthetic strategy allows a facile preparation of [2.2]paracyclophane derivatives featuring disparate para-substitutions at C-4 and C-7 positions in a highly selective manner, gives access to a series of potential candidates for [2.2]paracyclophane-derived new planar chiral ligands. The unprecedented behavior in reactivity and preferential selectivity of C-C coupling over C-N bond formation via C-H activation is unique to the [2.2]paracyclophane scaffold compared to the non-cyclophane analogue under the same reaction conditions. Selective C-H activation/aryl-aryl bond formation and sequential C-N coupling product formation is evidenced unambiguously by X-ray crystallography., (© 2020 The Authors. Published by Wiley-VCH GmbH.)