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Recent Advances in Metal-Catalyzed Alkyl–Boron (C(Sp3)–C(Sp2)) Suzuki-Miyaura Cross-Couplings

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Recent Advances in Metal-Catalyzed Alkyl–Boron (C(Sp3)–C(Sp2)) Suzuki-Miyaura Cross-Couplings catalysts Review Recent Advances in Metal-Catalyzed Alkyl–Boron (C(sp3)–C(sp2)) Suzuki-Miyaura Cross-Couplings 1, 2, 3 4 4 Janwa El-Maiss y, Tharwat Mohy El Dine y, Chung-Shin Lu , Iyad Karamé , Ali Kanj , Kyriaki Polychronopoulou 5,6,* and Janah Shaya 7,8,* 1 Université d’Orléans, Institut de Chimie Organique et Analytique, Pole Chimie, Rue de Chartres, 45000 Orléans, France; [email protected] 2 Institut des Biomolécules Max Mousseron (IBMM), UMR 5247, École nationale supérieure de chimie de Montpellier (ENSCM), 240 Avenue du Professeur Emile Jeanbrau, 34090 Montpellier, France; [email protected] 3 Department of General Education, National Taichung University of Science and Technology, Taichung 404, Taiwan; [email protected] 4 Laboratory of Catalysis Organometallic and Materials (LCOM), Depart. of Chemistry, Faculty of Science I, Lebanese University-Hariri Campus, Hadath, Lebanon; [email protected] (I.K.); [email protected] (A.K.) 5 Department of Mechanical Engineering, Khalifa University of Science and Technology, Abu Dhabi, P.O. Box 127788, UAE 6 Center for Catalysis and Separation, Khalifa University of Science and Technology, Abu Dhabi, P.O. Box 127788, UAE 7 College of Arts and Sciences, Khalifa University, Abu Dhabi, P.O. Box 127788, UAE 8 College of Medicine and Health Sciences, Khalifa University, Abu Dhabi, P.O. Box 127788, UAE * Correspondence: [email protected] (K.P.); [email protected] (J.S.) J.E.-M. and T.M.E.D. contributed equally to this work and shall be considered Co-First authors. y Received: 25 January 2020; Accepted: 19 February 2020; Published: 5 March 2020 Abstract: Boron chemistry has evolved to become one of the most diverse and applied fields in organic synthesis and catalysis. Various valuable reactions such as hydroborylations and Suzuki–Miyaura cross-couplings (SMCs) are now considered as indispensable methods in the synthetic toolbox of researchers in academia and industry. The development of novel sterically- and electronically-demanding C(sp3)–Boron reagents and their subsequent metal-catalyzed cross-couplings attracts strong attention and serves in turn to expedite the wheel of innovative applications of otherwise challenging organic adducts in different fields. This review describes the significant progress in the utilization of classical and novel C(sp3)–B reagents (9-BBN and 9-MeO-9-BBN, trifluoroboronates, alkylboranes, alkylboronic acids, MIDA, etc.) as coupling partners in challenging metal-catalyzed C(sp3)–C(sp2) cross-coupling reactions, such as B-alkyl SMCs after 2001. Keywords: Suzuki–Miyaura cross-couplings; C(sp3) –C(sp2); alkylboron reagents; metal catalysis 1. Introduction Boron is a peculiar metalloid with fascinating chemical complexity. The unusual properties of boron stem from its three valence electrons, which can be easily torn away, favoring metallicity and making it electron-deficient, yet sufficiently localized and tightly bound to the nucleus, consequently allowing the insulating states to emerge [1]. Boron compounds have been intensively investigated for energy storage applications, particularly due to the relatively low atomic mass of boron (10.811 0.007 amu). ± The energy-related uses of boron compounds range from high-energy fuels for advanced aircrafts to boron–nitrogen–hydrogen compounds as hydrogen storage materials for fuel cells [2]. The rich Catalysts 2020, 10, 296; doi:10.3390/catal10030296 www.mdpi.com/journal/catalysts Catalysts 2020, 10, x FOR PEER REVIEW 2 of 24 Catalysts 2020, 10, 296 2 of 25 0.007 amu). The energy-related uses of boron compounds range from high-energy fuels for advanced aircrafts to boron–nitrogen–hydrogen compounds as hydrogen storage materials for fuel cells [2]. Thepioneering rich pioneering research onresearch boron resultedon boron in resulted the consecutive in the consecutive awarding of awarding two Nobel of Prizes two Nobel in chemistry Prizes in chemistry1976 and 1979 in 1976 [3,4 ].and 1979 [3,4]. Organoboron compoundscompounds (e.g., (e.g., boronic boronic acids, acids, boronic boronic esters andesters boronamides) and boronamides) generally generally comprise compriseat least one at carbon–boronleast one carbon–boron (C–B) bond (C–B) (Scheme bond1A) (Scheme [ 5–8]. Organoboron 1A) [5–8]. Organoboron compounds werecompounds initially were used initiallyin organic used synthesis in organic 60 years synthesis ago [9,10 60]. Everyears since, ago chemistries[9,10]. Ever involving since, chemistries such compounds involving continued such compoundsto advance untilcontinued these to reagents advance have until become these reagents one of the have most become diverse, one widely of the most studied diverse, and appliedwidely studiedfamilies and in catalysis applied andfamilies organic in catalysis synthesis and [10 organic,11]. Currently, synthesis they [10,11]. are engagedCurrently, in they numerous are engaged classic inand numerous important classic reactions and such important as hydroborations reactions such and Suzuki–Miyauraas hydroborations cross-couplings and Suzuki–Miyaura (SMCs), amongcross- couplingsothers [8]. (SMCs), The SMC among reaction others generally [8]. The involves SMC thereac conjoiningtion generally of an involves organoboron the conjoining reagent and of an organoboronorganic halide reagent or pseudohalide and an organic in the presence halide or of pseudohalide palladium (or otherin the relevant presence metal of palladium/ligand) as a(or catalyst other relevantand a base metal/ligand) for the activation as a catalyst of the boronand a base compound for the (Schemeactivation1B) of [ 5the–7 ,boron12]. Organoboron compound (Scheme compounds 1B) [5–7,12].have also Organoboron found several compounds applications have in pharmaceuticals also found several where applications boron-based in drugspharmaceuticals exemplify awhere novel boron-basedclass of molecules drugs for exemplify several biomedical a novel class applications of molecules as molecular for several imaging biomedical agents (opticalapplications/nuclear as molecularimaging) andimaging neutron agents capture (optical/nuclear therapy agents imaging) (BNCT), and neutron as well capture as therapeutic therapy agentsagents (anticancer,(BNCT), as wellantiviral, as therapeutic antibacterial, agents etc.) (anticancer, [13]. Likewise, antiviral, the utility antibacterial, and ubiquity etc.) of [13]. boron-based Likewise, compounds the utility haveand ubiquitybolstered of the boron-based development compound of agriculturals have bolstered and material the sciencesdevelopment [14,15 of]. agricultural Organoborane and polymers material scienceshave been [14,15]. investigated Organobo as electrolytesrane polymers for batteries,have been electro-active investigated materials,as electrolytes and supportedfor batteries, Lewis electro- acid activecatalysts materials, [16,17]. and supported Lewis acid catalysts [16,17]. A) Selected examples of organoboron compunds R R R OR R NR2 F MeN B B O B B R F R B O O OH OR NR2 F O Boronic Boronic Boronamides Organotrifluoroborates RB-MIDA acids esters B) SMC reaction metal/ligand catalytic system 1 2 1 2 R BXn + R Y R R Base R1, R2 = Aryl, Alkenyl, Alkyl Xn = (OH)2, (OR)2, F3K, etc. Y = Cl, Br, I, OTf, etc. Metal catalysts = [Pd], [Ni] or [Fe], [Co], [Ru], [Ag], etc. (less common) SchemeScheme 1. ((AA)) Examples Examples of of organoboron organoboron compounds, compounds, ( (B)) Suzuki–Miyaura Suzuki–Miyaura cro cross-couplingss-coupling reaction. Metal catalysis has has had had a a major impact impact on on numerous numerous research research fields fields from from energy, energy, biomass, biomass, environmental and water purification purification to synthesi synthesiss of otherwise challenging and even inaccessible materials and and medicinal medicinal adducts adducts [18–30]. [18–30]. In In line, line, the the intensive intensive research research in inmetal metal catalysis catalysis has has led led to significantto significant progress progress in inborylation borylation of of primary primary C(sp C(sp3)–H3)–H bonds bonds of of unfunctionalized unfunctionalized hydrocarbons, hydrocarbons, allowing accessaccess to to a varietya variety of C(sp of3 )–BC(sp reagents3)–B reagents and consequent and conseque breakthroughsnt breakthroughs in C(sp3)–C(sp,sp in C(sp2,sp3)–3) C(sp,spcross-couplings.2,sp3) cross-couplings. Comprehensive Comprehensive work has been work done has on been the development done on the development of an efficient ofsp an2 spefficient2 SMC; − sphowever,2−sp2 SMC; there however, have been there far have fewer been reports far onfewersp3 reportssp2 or spon3 spsp3−3spvariants2 or sp3− [sp313– variants38]. Among [31–38]. thedi Amongfferent − − thehybridized different boron hybridized reagents boron employed reagents in SMCs employed (e.g., aryl,in SMCs heteroaryl, (e.g., aryl, and vinylboronicheteroaryl, and acids vinylboronic and esters), acidsthe use and of organoboronesters), the use compounds of organo withboron alkyl compounds groups (sp3 withcarbon) alkyl was groups severely (sp limited3 carbon) inthese was couplingseverely limitedreactions in due these to competitive coupling sidereactions reactions due [39 to,40 comp]. Organometallicetitive side compoundsreactions [39,40]. that are Organometallic metalated at sp3 compoundscarbon atoms that and are especially metalated containing at sp3 carbonβ-hydrogen atoms and atoms especially give rise containing to alkyl–palladium β-hydrogen complexes atoms give that Catalysts 2020, 10, 296 3 of 25 are susceptible to β-hydride
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