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.
Trang 1KHOA CÔNG NGHỆ HÓA HỌC
MÔN 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 hiện : TRẦN THỊ QUỲNH MAI
1
Trang 2Introduction and historical
overview of Sonogashira
reaction
Catalyst for Sonogashira reaction
Pd metal catalyst
Development of Pd metal Catalyst
Perspective and challenge of Pd catalyst
OUTLINE
1
2
3
4
5
Trang 3Organometallic
reagent
Oraganic electrophile
Synthetic transformation
Cross-coupling reactions
Động học xúc tác
Group 8-10 Metal Catalyst
C - C
Increase activity and stability of catalyst system
New halide, pseudohalides,
organometallic nucleophile
1 2
SP Nolan; O Navarro: C-C Bond Formation by Cross-Coupling, Reference Module in Chemistry, Molecular Sciences and Chemical Engineering, Elsevier,
2013, 1-32.
Trang 4Sonogashira reaction
Coupling of aryl/vinyl halides with terminal acetylenes catalyzed by Pd and other metals
Widely used sp2-sp C-C bond formation reactions
Synthesis of natural products, pharmaceuticals, molecular
organic chemistry
Rafeal Chinchilla; Carmen Najera: Recent Advances in Sonogashira reactions, Chem.Soc.Rev., 2011, 40, 5084-5121
Trang 5Its electronegativity
Easy access to Pd(II) and Pd(0)
oxidation states
Easy access to Pd(II) and Pd(0)
oxidation states
Formation of copper (I) acetylide
Air-sensitive and unwanted reactions
Trang 6Pd source _CuI_amine
Cu source
Pd source
Catalysts for sonogashira reaction
Beginning of 21st
2000-2013
Lately
Trang 7Động học xúc tác
Start PdCl2(PPh3)2
Reductive elimination
0 -2
+2
Oxidative addition
Cis/trans-isomerization
Reductive elimination
base
Start
Π-alkyne Cu
Rafeal Chinchilla; Carmen Najera: Recent Advances in Sonogashira reactions, Chem.Soc.Rev., 2011, 40,
5084-5121
Trang 8Pd(PPh₃)₄ Pd₂(PPh₃)₂
PALLADIUM SOURCE _copper (i) salt_amine
More stable
More soluble
Good for homogeneous conditions
Good for homogeneous conditions
Trang 92003
2005
Động học xúc tác
Herrmann et al
Palladacycle 100 mol ppm Without CuI
Santelli et al
Tedicyp 100 mol ppb
5 mol% CuI
cis,cis,cis-1,2,3,4- tetrakis(diphenylphosphinomethyl)-cyclopentane-[PdCl(eta3-C3H5)]2 system
turnover number of 2.600.000 can be obtained for the reaction of 4-trifluoromethylbromobenzene
with phenylacetylene in the presence of this catalyst.
12 publications for using catalyst loading of
≤ 100 mol ppm
David Roy and Yasuhiro Uozumi, Recent Advances in Palladium-Catalyzed Cross-Coupling Reactions at ppm to ppb Molar Catalyst Loadings Advanced Synthesis
& Catalysis, 2017, 1-27
Trang 10Copper based catalyst for
sonogashira reaction
Cu NPs
Anns Maria Thomas, et al Recent advances and perspectives in coppercatalyzed Sonogashira coupling reactions RSC Adv., 2014, 4, 21688
MECHANISM
Trang 11Copper-free sonogashira reaction
Động học xúc tác
Shortcoming:
- CuI-polyphosphane adducts can be formed
- Ligands can be transferred from one metal to other
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,
5084-5121
Trang 12Development of Palladium catalyst
Pd
Economic
Environment
Recovery
Reuse
Trang 13Pd catalyti
c system
Organ
ic polym er-suppo rted
Pd cataly
st
C-based mater ial-suppo rted
Pd cataly
st Funtiona lized silica-supporte
d Pd catalyst
Magn etic mater ial-suppo rted
Pd cataly
st
Hybri
d mater ial-suppo rted
Pd cataly
st
Inorg anic mater ial-suppo rted
Pd cataly
st
Outstanding palladium catalytic system
Động học xúc tác
Trang 14Outstanding palladium catalytic system
Organic
polymer-supported Pd
catalyst
Oldest support
Perform in copper-free
reaction
Perform in copper-free
reaction
PS-divinylbenzene resin beads
Yield: up to 99% Recovery 5 times
No additional solvent
Water as solvent
Trang 15Outstanding palladium catalytic system
Mainly PdNPs
Use of Copper Ligand: triphenylphosphine
Use of Copper Ligand: triphenylphosphine
Deactivate after several reaction
cycle
Deactivate after several reaction
cycle
Slow down aggregation of NPs
Covered Pd by another metal:
Au, Ni, Co, Cu
Covered Pd by another metal:
Au, Ni, Co, Cu
Higher catalytic activity C-based
material-supported Pd
catalyst
Support on graphene oxide, multi-walled CNT
Support on graphene oxide, multi-walled CNT
Reuse: 6 times
Trang 16Outstanding palladium catalytic system
Various types of silica material
Minimize metal leaching
Minimize metal leaching
Funtionalized silica-supported Pd catalyst
Chemical and mechanical
stability
Chemical and mechanical
stability
Reuse: max 6 times
Diferent functional
group
Diferent functional
group
Copper-free reaction
Trang 17Outstanding palladium catalytic system
Easy to separate from the
medium
Easy to separate from the
medium
Heterogeneous support
Iron (II) + iron (III) oxide in cubic inverse spinel structure
Iron (II) + iron (III) oxide in cubic inverse spinel structure
Magnetic
material-supported Pd
catalyst
Recycle: up to 10 times
Trang 18Outstanding palladium catalytic system
Reduce amount of metal requirement
Reduce amount of metal requirement
Heterogeneous support
Many hybrid: Ca-Ch, Cu@MgO, CDs,
organic framework
Many hybrid: Ca-Ch, Cu@MgO, CDs,
Hybrid
material-supported Pd
catalyst
Trang 19Pd complexes
Pd NPs
Supported Pd NPs
Conclusions
Conventional Sonogashira
Copper-free Sonogashira
↓ Recyclability is still not remarkable
↓ Only “easy” for aryl iodide
↓ Limit on broad application