Radical Amination of C(sp3)–H Bonds Using N‑Hydroxyphthalimide and Dialkyl Azodicarboxylate
A direct conversion of C(sp3)–H bonds to C(sp3)–N bonds has been achieved by utilizing catalytic N-hydroxyphthalimide (NHPI) and stoichiometric dialkyl azodicarboxylate. NHPI functions as a precursor of the electron-deficient phthalimide N-oxyl radical (PINO) to abstract hydrogens, and dialkyl azodi...
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Published in | Journal of organic chemistry Vol. 77; no. 22; pp. 9959 - 9969 |
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Main Authors | , , , |
Format | Journal Article |
Language | English |
Published |
WASHINGTON
American Chemical Society
16.11.2012
Amer Chemical Soc |
Subjects | |
Online Access | Get full text |
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Summary: | A direct conversion of C(sp3)–H bonds to C(sp3)–N bonds has been achieved by utilizing catalytic N-hydroxyphthalimide (NHPI) and stoichiometric dialkyl azodicarboxylate. NHPI functions as a precursor of the electron-deficient phthalimide N-oxyl radical (PINO) to abstract hydrogens, and dialkyl azodicarboxylate acts as a trapping agent of the resultant carbon radical to generate the hydrazine derivatives. This C–H amination proceeds in a highly chemoselective manner with a wide applicability to functionalize benzylic, propargylic, and aliphatic C–H bonds. Furthermore, the obtained hydrazine compounds were readily converted to the corresponding carbamates or amines. Hence, the present protocol for direct introduction of the nitrogen functionality serves as a powerful tool for efficient construction of nitrogen-substituted natural products and pharmaceuticals. |
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Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 0022-3263 1520-6904 |
DOI: | 10.1021/jo301840e |