PowerPoint Presentation A SHORT REVIEW ON PalLadium metal based catalyst for SONOGASHIRA reaction Giảng viên hướng dẫn GS TSKH LƯU CẨM LỘC Học viên thực hiện TRẦN THỊ QUỲNH MAI MSHV 17112501 1 TRƯỜNG ĐẠI HỌC CÔNG NGHIỆP TP HỒ CHÍ MINH KHOA CÔNG NGHỆ HÓA HỌC MÔN ĐỘNG HỌC XÚC TÁC OUTLINE 1 2 3 4 5 Động học xúc tác 2 2 Introduction and historical overview of Sonogashira reaction Catalyst for Sonogashira reaction Pd metal catalyst Development of Pd metal Catalyst Perspective and challenge of Pd cata.
TRƯỜNG ĐẠI HỌC CƠNG NGHIỆP TP HỒ CHÍ MINH KHOA CƠNG NGHỆ HĨA HỌC MƠN ĐỘNG HỌC XÚC TÁC A SHORT REVIEW ON PalLadium metal based catalyst for SONOGASHIRA reaction Giảng viên hướng dẫn : GS.TSKH LƯU CẨM LỘC Học viên thực : TRẦN THỊ QUỲNH MAI MSHV : 17112501 OUTLINE Perspective and challenge of Pd Sonogashira reaction Introduction and historical overview of Sonogashira reaction Động học xúc tác Development of Pd metal Catalyst Pd metal catalyst Catalyst for catalyst Cross-coupling reactions C-C Group 8-10 Metal Catalyst Organometallic Oraganic reagent electrophile Synthetic transformation C-H C-N C-O C-S C-P C-M New halide, pseudohalides, Increase activity and organometallic nucleophile stability of catalyst system Động học xúc tác SP Nolan; O Navarro: C-C Bond Formation by Cross-Coupling, Reference Module in Chemistry, Molecular Sciences and Chemical Engineering, Elsevier, 2013, 1-32 4 Sonogashira reaction Coupling of aryl/vinyl halides with terminal acetylenes catalyzed by Pd and other metals Widely used sp2-sp C-C bond formation reactions Rafeal Chinchilla; Carmen Najera: Recent Advances in Sonogashira reactions, Chem.Soc.Rev., 2011, 40, 5084-5121 Synthesis of natural products, pharmaceuticals, molecular organic chemistry Động học xúc tác Its electronegativity Formation of copper (I) acetylide Easy access to Pd(II) and Pd(0) Air-sensitive and unwanted reactions oxidation states Động học xúc tác Catalysts for sonogashira reaction Lately Pd source 2000-2013 Cu source Beginning of 21 st Pd source _CuI_amine Động học xúc tác Mechanism +2 -2 Reductive elimination Start Oxidative addition PdCl2(PPh3)2 Reductive elimination Cis/trans-isomerization Start base Π-alkyne Cu Động học xúc tác Rafeal Chinchilla; Carmen Najera: Recent Advances in Sonogashira reactions, Chem.Soc.Rev., 2011, 40, 50845121 PALLADIUM SOURCE _copper (i) salt_amine More stable More soluble others Pd₂(PPh₃)₂ Pd(PPh₃)₄ Good for homogeneous conditions Good for homogeneous conditions Động học xúc tác cis,cis,cis-1,2,3,4tetrakis(diphenylphosphinomethyl)cyclopentane-[PdCl(eta3-C3H5)]2 system 12 publications for using catalyst loading of ≤ 100 mol ppm Santelli et al Tedicyp 100 mol ppb 1999 mol% CuI Herrmann et al Palladacycle 100 mol ppm Without CuI 2005 2003 turnover number of 2.600.000 can be obtained for the reaction of 4-trifluoromethylbromobenzene with phenylacetylene in the presence of this catalyst David Roy and Yasuhiro Uozumi, Recent Advances in Palladium-Catalyzed Cross-Coupling Reactions at ppm to ppb Molar Catalyst Loadings Advanced Synthesis Động học xúc tác & Catalysis, 2017, 1-27 10 Copper based catalyst for sonogashira reaction Cu Nitrogen Cu Phosphorus Cu Oxygen MECHANISM Cu-N Oxygen Cu NPs Anns Maria Thomas, et al Recent advances and perspectives in coppercatalyzed Sonogashira coupling reactions RSC Adv., 2014, 4, 21688 Động học xúc tác 11 Copper-free sonogashira reaction Shortcoming: - CuI-polyphosphane adducts can be formed Ligands can be transferred from one metal to other Supposed mechanism for the copper-free Sonogashira reaction Rafeal Chinchilla; Carmen Najera: Recent Advances in Sonogashira reactions, Chem.Soc.Rev., 2011, 40, Động học xúc tác 5084-5121 12 Development of Palladium catalyst Economic Environment Động học xúc tác Pd Recovery Reuse 13 Outstanding palladium catalytic system Organ ic polym Inorg anic mater ialsuppo rted suppo rted Pd cataly st Cbased mater ialsuppo rted Pd Pd Pd Hybri cataly catalyti cataly d st c mater system ialsuppo rted Pd cataly st Động học xúc tác er- st Funtiona lized Magn silica- etic supporte mater d Pd ial- catalyst suppo rted Pd 14 Outstanding palladium catalytic system Oldest support Organic polymersupported Pd catalyst Recovery times Perform in copper-free Yield: up to 99% reaction No additional solvent PS-divinylbenzene resin beads Water as solvent Động học xúc tác 15 Outstanding palladium catalytic system Reuse: times Mainly PdNPs Higher catalytic activity C-based material- Use of Copper supported Pd Ligand: triphenylphosphine multi-walled CNT catalyst Động học xúc tác Support on graphene oxide, Deactivate after several reaction Covered Pd by another metal: cycle Au, Ni, Co, Cu Slow down aggregation of NPs 16 Outstanding palladium catalytic system Reuse: max times Various types of silica material Diferent functional Funtionalized silica- Minimize metal group supported Pd catalyst leaching Copper-free reaction Chemical and mechanical stability Động học xúc tác 17 Outstanding palladium catalytic system Easy to separate from the medium Magnetic materialsupported Pd Heterogeneous support catalyst Iron (II) + iron (III) oxide in cubic inverse spinel structure Động học xúc tác Recycle: up to 10 times 18 Outstanding palladium catalytic system Reduce amount of metal requirement Hybrid materialsupported Pd Heterogeneous support catalyst Many hybrid: Ca-Ch, Cu@MgO, CDs, organic framework Động học xúc tác Recycle: up to 13 times 19 Conclusions Copper-free Sonogashira Supported Pd NPs Pd NPs Conventional Sonogashira Pd complexes ↓ Recyclability is still not remarkable ↓ Only “easy” for aryl iodide ↓ Limit on broad application Động học xúc tác 20 Động học xúc tác ... Perspective and challenge of Pd Sonogashira reaction Introduction and historical overview of Sonogashira reaction Động học xúc tác Development of Pd metal Catalyst Pd metal catalyst Catalyst for catalyst. .. 4 Sonogashira reaction Coupling of aryl/vinyl halides with terminal acetylenes catalyzed by Pd and other metals Widely used sp2-sp C-C bond formation reactions Rafeal Chinchilla; Carmen Najera:... CuI-polyphosphane adducts can be formed Ligands can be transferred from one metal to other Supposed mechanism for the copper-free Sonogashira reaction Rafeal Chinchilla; Carmen Najera: Recent Advances in Sonogashira