C-H活化知识-文档资料

1、1Activation of Substrates in Activation of Substrates in Rhodium-Catalyzed C-H Rhodium-Catalyzed C-H FunctionalizationFunctionalizationXingwei LiDalian Institute of Chemical Physics, Chinese Academy of SciencesDec. 17, 20142The C-H Activation StrategyThe C-H Activation StrategyHigh step-economyReadi

2、ly available hydrocarbonsBroadened arsenal of retro-synthetic analysisM = Pd, Cu, Ni, Co, Rh, Ir, Ru, Mn, Re3Rhodium(III) Catalysisd6, 18 e-, 6-CoordinateRh(III) is usually the highest oxidation state. Cp*Rh(III) is less prone to decomposition.With a Cp* ligand and a cyclometalated substrate, only o

3、ne coordination site is available.ObjectivesNew reaction patternsDifferent selectivitiesHigher reactivityBroad scope/compatibilityGlorius, Adv. Synth. Catal. 2014 , 356, 1443. Li, Chem. Soc. Rev. 2012, 41, 3651.Satoh and Miura, Chem. Eur. J. 2010, 16, 11212. 4Two Activation StrategiesMore Ionic M +

4、C - BondHigher Reactivity toward Polar BondsAtom- and Step-Economic Surrogate to organo Main Group ReagentsNew PatternsGeneralityControllable Selectivity5Part 1: Activation of the AreneParticipating DGs-Coordinating Ability-Nucleophilicity/Electrophilicity DGNu/DGE+-Redox-Reactivity DGOX-Other Post-

5、Coupling TransferabilityShi, Angew. Chem. Int. Ed. 2012, 51, 3948.Cheng, Angew. Chem. Int. Ed. 2011, 50, 4169.Glorius, J. Am. Chem. Soc. 2011, 133, 2154.6In situ Generation of DGs/Activation of DGs7DG with Nucleophilicity8Angew. Chem. Int. Ed. 2012, 51, 11819.DG with Nucleophilicity: Azomethine Imin

6、e9Mechanistic StudiesKIE = 1.211Heterocycles: Different SelectivityAngew. Chem. Int. Ed. 2012, 51, 11819.12Sulfonamides: Multiple RolesAngew. Chem. Int. Ed. 2012, 51, 12348.13Sulfonamide: Substrate ScopeAngew. Chem. Int. Ed. 2012, 51, 12348.14Mechanism15Electrophilic DGs16DG with Redox-Reactivity: O

7、xidizing N-O GroupAngew. Chem. Int. Ed. 2011, 50, 7791-7796.17Angew. Chem. Int. Ed. 2014, 53, 10794.Internal Oxidizing N-O DGsMatsuo, Adv. Synth. Catal. 2014, 356, 1516.Angew. Chem. Int. Ed. 2014, 53, 10794.1920Unpublished Results21Oxidizing C-N Bonds: Our 1st Example2223collaboration with Prof. Yu

8、Lan 24Part 2.Activation of the Polar Coupling Partner25Umpolung: C-H AlkynylationJ. Am. Chem. Soc. 2014, 136, 4780.26J. Am. Chem. Soc. 2014, 136, 4780.Loh, Angew. Chem. Int. Ed. 2014,53, 2722.27Complementary Scope in Iridium CatalysisJ. Am. Chem. Soc. 2014, 136, 4780.28Path (a) is more likely. Umpol

9、ung: C-H AzidationAngew. Chem. Int. Ed. 2013, 52, 11862. 30Oxidative C-H AzidationAngew. Chem. Int. Ed. 2013, 53, 11862. with Fang Xie and Zisong Qi31Synthetic Applications of Azide Products32Umpolung: C-H Nitration33Umpolung: C-Heteroatom Formation34Activation by Ring Strain: Strained Olefins?氧杂/氮杂

10、苯并降冰片二烯35Angew. Chem. Int. Ed. 2013, 52, 8995.377-Oxabenzonorbornadienes: Redox-Neutral Dehydrative C-C Coupling Angew. Chem. Int. Ed. 2013, 52, 8995.38C-C Coupling with AziridinesAngew. Chem., Int. Ed. 2013, 52, 2577. with Songjie Yu39Mechanistic Studies403-Membered Rings41Coupling Driven by AromatizationOrg. Lett. 2014 , 16, 1586.42Summary43 Dr. Guoyong Song Dr. Miao Zhao Dr. Peng Zhao Dr. Fang Xie Jinlei Chen Xue Gong Fen Wang Zisong Qi Yuye ChenXingping ZhangXuting