Copper-catalyzed amidation of allylic and benzylic C-H bonds

Organic Letters

Volumn 8, Issue 26, 2006, Pages 6031-6034

  Pelletier, Guillaume ^a   Powell, David A ^a  

^a MERCK FROSST CENTRE FOR THERAPEUTIC RESEARCH   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

AMIDE; COPPER;

ARTICLE; CATALYSIS; CHEMISTRY;

AMIDES; CATALYSIS; COPPER;

EID: 33846128749     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol062514u     Document Type: Article

References (50)

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7. Representative intramolecular metal-nitrene-type amidations: (a) Kim, M.; Mulcahy, J. V.; Espino, C. G.; Du Bois, J. Org. Lett. 2006, 8, 1073-1076.
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39. A single example of a copper-catalyzed amidation of cyclohexene with phthalimide in the presence of tert-butyl hydroperoxide (14% yield) was described by Kharasch almost 50 years ago: Kharasch, M. S.; Fono, A. J. Org. Chem. 1958, 23, 325-326.
40. 2 and chloramine-T gave lower yields of product.
41. Yields in the absence of 1,10-phenanthroline ligand are only slightly lower (64% by HPLC); however, use of an excess of ligand (20 mol %) results in dramatically diminished yields.
42. 2 catalyst may be deactivated or decomposing in the presence of an excess of the oxidant.
43. 6b.
44. For those reactions that proceeded in only moderate yield, the remaining mass balance consisted of primarily the sulfonamide and hydrocarbon starting materials.
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48. A third mechanistic possibility involves oxidation of the hydrocarbon species to an alkene, followed by a copper-catalyzed hydroamination, although diphenylmethane and adamantane, for which alkene intermediates are unlikely, are reactive under our conditions. See: Taylor, J. G.; Whittall, N.; Hu, K. K. Org. Lett. 2006, 8, 3561-3564.
49. To our knowledge, this copper-catalyzed amidation reaction of a benzylic acetate has not previously been observed; however, copper-catalyzed animations of allylic halides are known. See: Baruah, J. B.; Samuelson, A. G. Tetrahedron 1991, 47, 9449-9454.
50. Under the optimized conditions described in table 1, amidation of indane with benzamide or tert-butyl carbamate proceeds in only 5% and 12% yields, respectively.