title: Toward a synthetically useful stereoselective C-H amination of hydrocarbons.
abstract: Reaction between a sulfur(VI) compound and an iodine(III) oxidant in the presence of a catalytic quantity (<=3 mol %) of a rhodium(II) catalyst leads to the formation of a chiral metallanitrene of unprecedented reactivity. The latter allows intermolecular C-H amination to proceed in very high yields up to 92% and excellent diastereoselectivities up to 99% with C-H bond containing starting materials as the limiting component. The scope of this C-H functionalization includes benzylic and allylic substrates as well as alkanes. Secondary positions react preferentially, but insertion into activated primary C-H bonds or sterically accessible tertiary sites is also possible. Cooperative effects between the nitrene precursor and the chiral catalyst at the origin of these good results have also been applied to kinetic resolution of racemic sulfonimidamide. This methodology paves the way to the use of Csp3-H bonds as synthetic precursors for the introduction of a nitrogen functionality into selected positions.
authors: Institut de Chimie des Substances Naturelles, UPR 2301, CNRS, Avenue de la Terrasse, F-91198 Gif-sur-Yvette, France.
authors: Chungen
authors: C
authors: Liang
authors: Florence
authors: F
authors: Collet
authors: Fabien
authors: F
authors: Robert-Peillard
authors: Paul
authors: P
authors: Müller
authors: Robert H
authors: RH
authors: Dodd
authors: Philippe
authors: P
authors: Dauban
mesh_terms: D000586:Amination; D000588:Amines / Q000138:chemical synthesis*; D006838:Hydrocarbons / Q000737:chemistry*; D007097:Imines / Q000138:chemical synthesis* / Q000737:chemistry; D007455:Iodine; D008722:Methods; D009584:Nitrogen / Q000737:chemistry; D013237:Stereoisomerism; D013455:Sulfur
chemical_list: D000588:Amines; D006838:Hydrocarbons; D007097:Imines; C017621:phenylnitrene; D013455:Sulfur; D007455:Iodine; D009584:Nitrogen