Cross-Dehydrogenative Coupling (CDC):
Exploring C-C Bond Formations beyond
Functional Group Transformations
Lit. seminar 2010/07/24
M2 JianYi Wang

Professional Experience
2003-2002 (Fall)
2000-2003

Prof. Chao-Jun Li

1998-2000
1994-1998
1992-1994
1989-1992
1985-1988
1979-1983

Professor of Chemistry
Canada Research Chair (Tier I) in Organic/Green Chemistry
Department of Chemistry, McGill University, Montreal,
CanadaVisiting Professor
Department of Chemistry, University of California, Berkeley,
USA
Professor of Chemistry
Department of Chemistry, Tulane University, New Orleans,
USA
Associate Professor (with Tenure)Department of Chemistry, Tulane University, New Orleans,USAAssistant Professor
Department of Chemistry, Tulane University, New Orleans,
USA
NSERC Post-Doctoral Fellow
Stanford University; Advisor: Prof. B. M. Trost
Ph.D. Organic Chemistry
McGill University; Advisors: Prof. Tak-Hang Chan and Prof.
David N. Harpp
M.S. Organic Chemistry
Chinese Academy of Science; Advisor : Prof. Tak-Hang
Chan (McGill University)
B.S. Chemistry
Zhengzhou University, China

Contents:
Introduction
Background
CDC Recation Involving ¦Á-C-H Bonds of Nitrogen in Amines
Alkynylation (sp3-sp Coupling).
Arylation (sp3-sp2 Coupling).
Alkylation (sp3-sp3).
CDC Reaction of ¦Á-C-H Bonds of Oxygen in Ether (sp3-sp3)
CDC Reaction of Allylic and Benzylic C-H Bonds
Allylic Alkylation (sp3-sp3).
Benzylic Alkylation (sp3-sp3).
CDC Reaction of Alkane C-H Bonds
Alkane Alkylation (sp3-sp3).
Alkane Arylation (sp3-sp2).
Conclusion and Outlook

Introduction and BackgroundResearch in three progressive stages(1) developing Grignard-type reactions in aqueous media
to simplify protection-deprotection steps.
(2) developing nucleophilic addition reactions by using C-H bonds
as surrogates for organometallic reagents to simplify halogenationdehalogenation steps and avoid the utilization of a stoichiometricamount of metal for such reactions (possible in water)(3) developing direct C-H and C-H coupling to explore the possibilityof chemical transformations beyond functionalization anddefunctionalization in syntheses.

Chao-Jun Li, J. AM. CHEM. SOC. 2005, 105, 3095

Chao-Jun Li, J. AM. CHEM. SOC. 2007, 106, 2546

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CDC Reaction Involving ¦Á-C-H Bonds of Nitrogen in Amines
Alkynylation (sp3-sp Coupling)

Starting Point:(1) propargylic amines are of great pharmaceutical interest and are synthetic intermediates for various nitrogen compounds;(2) the sp3 C-H bond ¦Á to nitrogen in amines can be readily activated to generate iminium ions via single-electron-transfer (SET)
processes or by transition metals as described by Leonard and Murahashi;(3) we and others have described the aldehyde-alkyne-amine coupling (A3) reactions to afford propargyl amines catalyzed by varioustransition metals via the formation of the same intermediate (Scheme 2).

Chao-Jun Li, J. AM. CHEM. SOC. 2004, 126, 11810-11811

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Chao-Jun Li, Org. Lett., Vol. 6, No. 26, 2004

Chao-Jun Li, Angew. chem. int. Ed. 2008, 47, 7075-7078

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Arylation (sp3-sp2 Coupling).

Chao-Jun Li, J. AM. CHEM. SOC. 2005, 127, 6968-6969

Chao-Jun Li, PANS 2006, 103, 8928-8933

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Alkylation (sp3-sp3).

Chao-Jun Li, J. AM. CHEM. SOC. 2005, 127, 3672-3673

Chao-Jun Li, Green Chem, 2007, 9, 1047-1050

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Chao-Jun Li, PANS 2006, 103, 8928-8933

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CDC Reaction of ¦Á-C-H Bondsof Oxygen in Ethers (sp3-sp3)

Chao-Jun Li, Angew. Chem. Int. Ed. 2006, 45, 1949-1952

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Chao-Jun Li, J. AM. CHEM. SOC. 2006, 128, 4242-4243

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CDC Reaction of Allylic and Benzylic C-H Bonds
Allylic Alkylation (sp3-sp3).

Chao-Jun Li, J. AM. CHEM. SOC. 2006, 128, 56-57

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Benzylic Alkylation (sp3-sp3).

Chao-Jun Li, Angew. Chem. Int. Ed. 2007, 46, 6505-6507

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CDC Reaction of Alkane C-H Bonds
Alkane Alkylation (sp3-sp3).

Chao-Jun Li, Eur. J. Org. Chem. 2007, 4654-4657

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Alkane Arylation (sp3-sp2).

Chao-Jun Li, J. AM. CHEM. SOC. 2008, 130, 2900-2901

Chao-Jun Li, Angew. Chem. Int. Ed. 2008, 47, 6278-6282

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