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Photoinduced, copper-catalyzed alkylation of amides with unactivated secondary alkyl halides at room temperature
Citation
Do, H-Q and Bachman, S and Bissember, AC and Peters, JC and Fu, GC, Photoinduced, copper-catalyzed alkylation of amides with unactivated secondary alkyl halides at room temperature, Journal of the American Chemical Society, 136, (5) pp. 2162-2167. ISSN 0002-7863 (2014) [Refereed Article]
Copyright Statement
Copyright 2014 American Chemical Society
Abstract
The development of a mild and general method for the
alkylation of amides with relatively unreactive alkyl halides (i.e., poor substrates
for SN2 reactions) is an ongoing challenge in organic synthesis. We describe
herein a versatile transition-metal-catalyzed approach: in particular, a photoinduced,
copper-catalyzed monoalkylation of primary amides. A broad array of
alkyl and aryl amides (as well as a lactam and a 2-oxazolidinone) couple with unactivated secondary (and hindered primary) alkyl
bromides and iodides using a single set of comparatively simple and mild conditions: inexpensive CuI as the catalyst, no separate
added ligand, and C−N bond formation at room temperature. The method is compatible with a variety of functional groups,
such as an olefin, a carbamate, a thiophene, and a pyridine, and it has been applied to the synthesis of an opioid receptor
antagonist. A range of mechanistic observations, including reactivity and stereochemical studies, are consistent with a coupling
pathway that includes photoexcitation of a copper−amidate complex, followed by electron transfer to form an alkyl radical.
Item Details
Item Type: | Refereed Article |
---|---|
Research Division: | Chemical Sciences |
Research Group: | Organic chemistry |
Research Field: | Organic chemical synthesis |
Objective Division: | Expanding Knowledge |
Objective Group: | Expanding knowledge |
Objective Field: | Expanding knowledge in the chemical sciences |
UTAS Author: | Bissember, AC (Associate Professor Alex Bissember) |
ID Code: | 89088 |
Year Published: | 2014 |
Web of Science® Times Cited: | 148 |
Deposited By: | Chemistry |
Deposited On: | 2014-02-25 |
Last Modified: | 2017-10-25 |
Downloads: | 0 |
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