Transition-metal Catalyzed Intramolecular Amination of the
C(sp3)-H Bonds
Reporter: Ying Chen March 2nd, 2014
http://www.chem.psu.edu/directory/guc11
Research Interests: Analytical Fluorescence Imaging of Protein Trafficking in Live Cells Organic Synthetic and Biological Studies of Carbohydrates and Peptides Biological Chemical Biology of Carbohydrates and Peptides Materials and Nanoscience Nano Material for Molecular Imaging in Live Cells
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Syntheses of Azetidines via Intramolecular Amination of C(sp3)-H at ɤ Position
J. AM. CHEM. SOC. 2005,127, 13154-13155 3
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Syntheses of Pyrrolidines via Intramolecular Amination of C(sp3)-H at δ Position
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Syntheses of Indolines via Intramolecular Amination of C(sp2)-H at δ Position
Substrate Deuteration Studies
Reactivities of different C(sp3)−H bonds: Primary γ-C−H > primary δ-C−H > secondary and tertiary γ-C−H bonds 6
Use of a Readily Removable Auxiliary Group for the Synthesis of Pyrrolidones by the Palladium-Catalyzed Intramolecular Amination of Unactivatedg C(sp3)-H Bonds
Angew. Chem. Int. Ed.2013, 52, 1 – 6
Gang He, Shu-Yu Zhang, William A. Nack, Qiong Li, and Gong Chen
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B. V. S. Reddy, L. R. Reddy, E. J. Corey, Org. Lett.2006, 8, 3391.
N-Phth
AQ
Original Proposal
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Intramolecular amination of ɤ C(sp3)-H bonds via a six-membered palladacycle
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Both AQ- and PM- directed intramolecular ɤ-C(sp3)-H amination reactions proceeded well if the kinetic inertness of the initial ɤ-C-H palladation could be overcome effectively. 10
Application
Removal of the auxiliary group
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第2弾
Angew. Chem. Int. Ed.2014, 53,1–5
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The first copper-catalyzed intramolecular C (sp3)-H [and C (sp2)-H] amidation using bidentate DG
The reaction proceeded at a terminal methyl group, as well as at the internal benzylic position of an alkyl chain.
C(sp3)-H C(sp2)-H
terminal methyl benzylic position
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The proposed mechanism
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Deuterium-labeling experiment
The kinetic isotope effect value was 2.6, thus supporting our notion that C-H bond activation is the rate-determining step.
C (sp2)-H selective reaction pathway
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