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.

The selective functionalization of a CÀH bond is an area of intense investigation as such a reaction leads to the formation of valuable building blocks from simple molecules.[1] Considering the ubiquity of CÀH bonds in organic compounds, the search for a process that allows their selective transformation remains challenging. Methodologies have been recently developed for regioselective CÀC, [2] CÀO, [3] or CÀN [4,5] bond formations that have found applications in total synthesis. [6] In the case of CÀH amination, significant results have been obtained by using transition-metal-catalyzed nitrene transfer that starts from iminoiodanes. [5,7] This field, pioneered by Breslow [8] and Mansuy, [9] has progressed considerably over the last five years with the discovery of new methodologies for the generation [5a,d, 10] of these hypervalent iodine(III) reagents in situ. Thus, PhI(OAc) 2 -mediated CÀH amination has been shown to be catalyzed by ruthenium,

The development of 3D printing in recent years opens up a vast array of possibilities in the field of flow analysis. In the present study, a new 3D-printed flow system has been developed for the selective spectrophotometric determination of lead in natural waters. This system was composed of three 3D-printed units (sample treatment, mixing coil and detection) that might have been assembled without any tubing to form a complete flow system. Lead was determined in a two-step procedure. A preconcentration of lead was first carried out on TrisKem Pb Resin located in a 3D-printed column reservoir closed by a tapped screw. This resin showed a high extraction selectivity for lead over many tested potential interfering metals. In a second step, lead was eluted by ammonium oxalate in presence of 4-(2-pyridylazo)-resorcinol (PAR), and spectrophotometrically detected at 520nm. The optimized flow system has exhibited a linear response from 3 to 120µgL. Detection limit, coefficient of variation and sampling rate were evaluated at 2.7µgL, 5.4% (n=6) and 4 sampleh, respectively. This flow system stands out by its fully 3D design, portability and simplicity for low cost analysis of lead in natural waters.