Abstract:Introduction
Halogenation in Presence of Solid Supports or Catalysts
Halogen Exchange and Transhalogenation Reactions
Oxyhalogenations
Cohalogenation and Mixed Halogenation
Halogen–Halogen Reagents
Carbon–Halogen Reagents
Nitrogen–Halogen and Phosphorus–Halogen Reagents
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“…Halogens play a crucial role in complex biological processes, such as ligand binding or molecular folding. − Oftentimes, these events are facilitated by directional secondary interactions, where the halogen acts either as an electron acceptor unit (i.e., halogen bonding) − or as a Lewis-basic hydrogen bond acceptor. − In addition to natural systems, halogens are common structural elements of numerous organic and inorganic compounds, conferring them unique physicochemical properties. , For example, the relevance of halogens in synthetic materials (e.g., polyfluorinated coatings, , polybrominated flame-retardants , ), pharmaceuticals, , pesticides, and other applications (e.g., catalysis) − has been widely documented. Additionally, halogens are well-known supramolecular synthons that have been used in different fields, such as anion binding, gels, , liquid crystals, , crystal engineering, and others. , More specifically, supramolecular polymers − have recently been recognized as important 1D/2D model systems that can shed light on various aspects of far more complex 3D crystallization processes. − This is due to the fact that their dynamic self-assembly into different molecular packings is strongly influenced by kinetic effects.…”
Halogens play a crucial role in numerous natural processes and synthetic materials due to their unique physicochemical properties and the diverse interactions they can engage in. In the field of supramolecular polymerization, however, halogen effects remain poorly understood, and investigations have been restricted to halogen bonding or the inclusion of polyfluorinated side groups. Recent contributions from our group have revealed that chlorine ligands greatly influence molecular packing and pathway complexity phenomena of various metal complexes. These results prompted us to explore the role of the halogen nature on supramolecular polymerization, a phenomenon that has remained unexplored to date. To address this issue, we have designed a series of archetypal bispyridyldihalogen Pt II complexes bearing chlorine (1), bromine (2), or iodine (3) and systematically compared their supramolecular polymerization in nonpolar media using various experimental methods and theory. Our studies reveal a remarkably different supramolecular polymerization for the three compounds, which can undergo two competing pathways with either slipped (kinetic) or parallel (thermodynamic) molecular packing. The halogen exerts an inverse effect on the energetic levels of the two self-assembled states, resulting in a single thermodynamic pathway for 3, a transient kinetic species for 2, and a hidden thermodynamic state for 1. This seesaw-like bias of the energy landscape can be traced back to the involvement of the halogens in weak N−H•••X hydrogen-bonding interactions in the kinetic pathway, whereas in the thermodynamic pathway the halogens are not engaged in the stabilizing interaction motif but rather amplify solvophobic effects.
“…Halogens play a crucial role in complex biological processes, such as ligand binding or molecular folding. − Oftentimes, these events are facilitated by directional secondary interactions, where the halogen acts either as an electron acceptor unit (i.e., halogen bonding) − or as a Lewis-basic hydrogen bond acceptor. − In addition to natural systems, halogens are common structural elements of numerous organic and inorganic compounds, conferring them unique physicochemical properties. , For example, the relevance of halogens in synthetic materials (e.g., polyfluorinated coatings, , polybrominated flame-retardants , ), pharmaceuticals, , pesticides, and other applications (e.g., catalysis) − has been widely documented. Additionally, halogens are well-known supramolecular synthons that have been used in different fields, such as anion binding, gels, , liquid crystals, , crystal engineering, and others. , More specifically, supramolecular polymers − have recently been recognized as important 1D/2D model systems that can shed light on various aspects of far more complex 3D crystallization processes. − This is due to the fact that their dynamic self-assembly into different molecular packings is strongly influenced by kinetic effects.…”
Halogens play a crucial role in numerous natural processes and synthetic materials due to their unique physicochemical properties and the diverse interactions they can engage in. In the field of supramolecular polymerization, however, halogen effects remain poorly understood, and investigations have been restricted to halogen bonding or the inclusion of polyfluorinated side groups. Recent contributions from our group have revealed that chlorine ligands greatly influence molecular packing and pathway complexity phenomena of various metal complexes. These results prompted us to explore the role of the halogen nature on supramolecular polymerization, a phenomenon that has remained unexplored to date. To address this issue, we have designed a series of archetypal bispyridyldihalogen Pt II complexes bearing chlorine (1), bromine (2), or iodine (3) and systematically compared their supramolecular polymerization in nonpolar media using various experimental methods and theory. Our studies reveal a remarkably different supramolecular polymerization for the three compounds, which can undergo two competing pathways with either slipped (kinetic) or parallel (thermodynamic) molecular packing. The halogen exerts an inverse effect on the energetic levels of the two self-assembled states, resulting in a single thermodynamic pathway for 3, a transient kinetic species for 2, and a hidden thermodynamic state for 1. This seesaw-like bias of the energy landscape can be traced back to the involvement of the halogens in weak N−H•••X hydrogen-bonding interactions in the kinetic pathway, whereas in the thermodynamic pathway the halogens are not engaged in the stabilizing interaction motif but rather amplify solvophobic effects.
“…Among the available protocols for carbon-halogen bond formation, synchronized to the numerous transition-metal-free strategies, [7] transition-metal-catalyzed selective CÀ X bond formation [8] in environmentally benign, operationally simple, atom and cost-effective manner has been an essential and challenging aspect of organic chemistry. [9] In the quest of atom and step economic access of highly functionalized organic molecules associated with the formation of new carbon-carbon and carbonheteroatom bonds, development of novel strategies for the efficient and straight forward difunctionalization of carbon-carbon multiple bonds have gained much popularity among the researchers from both academia and industry. To date, a wide variety of 1,2-difunctionalization protocols [10] including transition-metal-catalyzed CÀ H activation [11] have been developed.…”
Transition-metal-catalyzed 1,2-carbohalofunctionalization reactions of CÀ C multiple bonds have emerged rapidly over the past decade as a powerful tool for generating a new carbon-carbon and carbon-halogen bond via transposition of an existing carbon-halogen σ bond. Exploring this highly efficient mode of carbon-carbon multiple bond difunctionalization, various research groups have established novel strategies for the synthesis of organohalides by utilizing wide variety of transition metal catalysts under mild reaction conditions, avoiding stoichiometric waste of by-products, and with improved levels of chemo-, regio-, and stereoselectivities. Most of the 1,2-carbohalo-functionalization reactions involve either the carbon-halogen reductive elimination mechanism or the atom transfer radical addition (ATRA) mechanism. This review summarizes the recent progress in the area of transitionmetal-catalyzed intra-and intermolecular 1,2-carbo-halo-functionalization reactions of carbon-carbon multiple bonds and explicates the underlying potentiality and challenges within the field.
“…[9] Consequently, the extensive use of organic halides in organic synthesis is highly reliant on the availability of suitable and operationally simple methods for the selective installation of the halogen functionality into different organic substrates. [10] Over the years, continuous interest from synthetic chemists has led to the development of milder and environmentally benign procedures using transition metal catalysts for the synthesis of carbon-halogen bonds with excellent levels of selectivity. [11] In the last four decades, transition metal catalyzed CÀH activation has emerged as one of the most promising and step economic approaches to generate highly functionalized molecules.…”
The high importance of organic halides as synthetic precursors has led to the development of milder and environmentally benign methods for their synthesis. In this regard, transition metal catalyzed C−H activation has emerged as one of the most promising methods for the synthesis of organic halides with high atom economy and excellent stereo‐ and regio‐control. Despite the dominance of palladium and copper catalysts in the field of C−H halogenation reactions, iridium‐, rhodium‐ and cobalt‐complexes have also recently been employed as highly efficient catalysts for the formation of carbon‐halogen bonds. This review describes the current state of the art in the field of C−H halogenation reactions using group nine transition metal (Co, Rh, Ir) catalysts.
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