Rhodium-Catalyzed C-H Activation and Functionalization of Arenes: Scope, Selectivity, and Mechanism

TopicRhodium-Catalyzed C-H Activation and Functionalization of Arenes: Scope, Selectivity, and Mechanism

Speaker Researcher李兴伟 , DICP

Time2014.3.19  pm  3:30 --- 5:00
Location
701#B501

 

Introduction to the speaker:

Education

2001 – 2005                Ph. D (2005) and M. S. (2005) in inorganic chemistry, Yale University

                                    Advisor: Robert H. Crabtree

1999 – 2001                Graduate study, State University of New York at Albany (school transferring to Yale)

1991 – 1996                B. S. (1996) in chemistry, Fudan University, China


Professional Experience

2010-present                Professor of Chemistry (the 100-Talent Program), Dalian Institute of Chemical Physics, Chinese Academyof Sciences

2008 – 2009                Assistant Professor of Catalysis, The Scripps Research Institute, Scripps Florida

2006 – 2008                Assistant Professor, Nanyang Technological University, Singapore

2005 – 2006                Postdoctoral Scholar, California Institute of Technology, advisor: John E. Bercaw

Award

           2012             Research Award, Dalian Institute of Chemical Physics, Chinese Academy of Sciences

2005              Richard Wolfgang Prize for Best Ph. D. Thesis, Graduate School of Arts and

Sciences, Yale University

2002              Rhodium Bicentennial Fellowship from the Johnson Matthey Co.

2001               The Benjamin Smith Scholarship, State University of New York at Albany.


Research Experience

(1)   Catalysis

-          Design of metal catalysts for new organic transformations

-          Transition metal (rhodium and palladium) catalyzed oxidative C-C, C-O, and C-N coupling based on C-H activation  

-          Synthesis of heterocycles via metal catalyzed reaction methodologies

-          Selective activation and oxidation of C-H bonds, oxidation of methane to methanol

-          C-C coupling reactions involving alkynes.

-          Alkyne and alkene hydroamination

-          Anaerobic oxidation (dehydrogenation) of alcohols and other hydrogen-transfer reactions involving alcohols and amines.

(2)   Synthetic organometallic chemistry

-          Synthesis of metal complexes of Rh, Ir, Ru, Pt, and Pd, particularly with N-heterocyclic carbenes (NHC)

-          Synthesis of complexes with abnormal binding modes of N-Heterocyclic Carbenes

-          Synthesis and reactivity of protic N-heterocyclic carbenes

-          Synthesis of late transition metal complexes featuring multi-dentate ligands with flexible binding modes.

-          Structural and reactivity studies

(3)   Mechanistic organometallic chemistry

-          Inter- and intramolecular activation of C-H and C-C bonds.

-          Metal-ligand cooperation/interactions in organometallic chemistry

-          Hydrogen transfer reactions (hydrogenation, dehydrogenation, and transfer hydrogenation)

-          Research methods: dynamic NMR spectroscopy, intermediate isolation, X-ray crystallography, isotope labeling, and reaction kinetics.


Abstract

Metal-catalyzed C-H activation has been widely established as an important strategy in the functionalization of sp2 hybridized C-H bonds. In our studies, under oxidative or redox-neutral conditions, stable rhodium(III) complexes have been successfully applied to the C-H activation of arenes and olefins in the coupling with substrates such as alkenes, alkynes, strained rings, metal azides, and electrophilic amidating reagents. In these C-C and C-N coupling reactions, and Rh(III) catalysis has allowed the functionalization of a broad scope of arenes bearing a chelating group with high reactivity, broad substrate scope, and high functional group compatibility. The scope, selectivity, and mechanism of these reactions are discussed.