Substrate and catalyst effects in C–H insertion reactions of α-diazoacetamides. Issue 49 (7th December 2016)

• Record Type: Journal Article
• Authors: Ring, Aoife; Ford, Alan; Maguire, Anita R.
• Is Part Of: Tetrahedron letters. Volume 57:Issue 49(2016)
• Page Start: 5399
• Page End: 5406
• Publication Date: 2016-12-07
• Subjects: acam acetamidate -- cap caprolactamate -- esp α, α, α′, α′-tetramethyl-1, 3-benzenedipropionate -- 4(S)-MACIM methyl 1-acetyl-2-oxoimidazolidine-4(S)-carboxylate -- 4(S)-MEOX methyl 2-oxazolidone-4(S)-carboxylate -- 5(S)-MEPY methyl 2-pyrrolidone-5(S)-carboxylate -- oct octanoate -- pfb perfluorobutyrate -- PTTL N-phthaloyl-tert-leucinate; C–H insertion -- Diazoacetamides -- Catalyst effects -- β-Lactams -- γ-Lactams; Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1016/j.tetlet.2016.10.081
• Languages: English
• ISSNs: 0040-4039

Abstract

Graphical abstract: Highlights: Metal-carbene C–H insertion of diazoacetamides leads to the formation of lactams. Substrate and catalyst effects determine reactivity and selectivity. Excellent chemo-, regio- and stereocontrol can be achieved. Abstract: Intramolecular C–H insertion reactions of α-diazocarbonyl compounds typically proceed with preferential five-membered ring formation. However, the presence of a heteroatom such as nitrogen can activate an adjacent C–H site towards insertion resulting in regiocontrol issues. In the case of α-diazoacetamide derivatives, both β- and γ-lactam products are possible owing to this activating effect. Both β- and γ-lactam products are powerful synthetic building blocks in the area of organic synthesis, as well as a common scaffold in a range of natural and pharmaceutical products and therefore C–H insertion reactions to form such compounds are attractive processes.