C-H活化知识.pptx

Activation of Substrates in Rhodium-Catalyzed C-H Functionalization Xingwei Li Dalian Institute of Chemical Physics, Chinese Academy of Sciences Dec. 17, 2014 1 The C-H Activation Strategy High step-economy Readily available hydrocarbons Broadened arsenal of retro-synthetic analysis 2 M = Pd, Cu, Ni, Co, Rh, Ir, Ru, Mn, Re… Rhodium(III) Catalysis d6, 18 e-, 6-Coordinate Rh(III) is usually the highest oxidation state. Cp*Rh(III) is less prone to decomposition. With a Cp* ligand and a cyclometalated substrate, only one coordination site is available. 3 Objectives New reaction patterns Different selectivities Higher reactivity Broad scope/compatibility Glorius, Adv. Synth. Catal. 2014 , 356, 1443. Li, Chem. Soc. Rev. 2012, 41, 3651. Satoh and Miura, Chem. Eur. J. 2010, 16, 11212. Two Activation Strategies 4 More Ionic M+C- Bond Higher Reactivity toward Polar Bonds Atom- and Step-Economic Surrogate to organo Main Group Reagents New Patterns Generality Controllable Selectivity Part 1: Activation of the Arene Participating DGs -Coordinating Ability -Nucleophilicity/Electrophilicity [DGNu/DGE+] -Redox-Reactivity [DGOX] -Other Post-Coupling Transferability 5 Shi, Angew. Chem. Int. Ed. 2012, 51, 3948. Cheng, Angew. Chem. Int. Ed. 2011, 50, 4169. Glorius, J. Am. Chem. Soc. 2011, 133, 2154. 6 In situ Generation of DGs/Activation of DGs 7 DG with Nucleophilicity Angew. Chem. Int. Ed. 2012, 51, 11819. 8 DG with Nucleophilicity: Azomethine Imine Mechanistic Studies 9 KIE = 1.2 11 Heterocycles: Different Selectivity Angew. Chem. Int. Ed. 2012, 51, 11819. Sulfonamides: Multiple Roles 12 Angew. Chem. Int. Ed. 2012, 51, 12348. 13 Sulfonamide: Substrate Scope Angew. Chem. Int. Ed. 2012, 51, 12348. Mechanism 14 15 Electrophilic DGs 16 DG with Redox-Reactivity: Oxidizing N-O Group Angew. Chem. Int. Ed. 2011, 50, 7791-7796. 17 Angew. Chem. Int. Ed. 2014, 53, 10794. Internal Oxidizing N-O DGs Matsuo, Adv. Synth. Catal. 2014, 356, 1516. Angew. Chem. Int. Ed. 2014, 53, 10794.