Mixed-metal reagents [NaMg(CH2SiMe3)3] (1) and [(THF)NaMg(NPh2)3(THF)] [3-(THF)(2)] can act as precatalysts to selectively promote the hydroamination/trimerization of isocyanates (RNCO) depending on the steric bulk of the R substituent.

Opening-up new synthetic applications of beta-diketiminate stabilised magnesium complexes, this case study compares the ability of the alkyl [{Ar*NC(Me)CHC(Me)NAr*}Mg(Bu)(THF)] (1) and the amido reagent [{Ar*NC(Me)CHC(Me)NAr*}Mg(TMP)] (2) (Ar* = 2,6-i- Pr-2-C6H3) to promote direct Mg-H exchange towards the series of 1,3-benzoazoles: benzoxazole (boz), benzothiazole (btz) and N-methyl benzimidazole (blm(Me)). Both reagents deprotonate boz at room temperature to yield [{Ar*NC(Me)CHC(Me)NAr*} Mg{O(o-C6H4) NC}(THF)] (3) via the C-O bond cleavage of a putative C2-magnesiated-benzoxazolyl intermediate. Structurally tracking the reactivity of 1 and 2 towards less acidic btz and blm(Me) showed that the behaviour of reagents 1 and 2 diverged dramatically. Kinetically activated TMP-reagent 2 effectively promotes the deprotonative magnesiation of btz and blm(Me) under mild reaction conditions, giving the alpha-metallated intermediates [{Ar* NC(Me) CHC(Me)NAr*}(2)Mg-2{btz*}(2)] (4) and [{Ar*NC(Me)CHC(Me)NAr*}(2)Mg-2{blm(Me)*}(2)] (7) (btz* = 2-benzothiazolyl; blm(Me)* = 2-N-methylbenzimidazolyl). Analysis of crystallographic and NMR data revealed that in 4 and 7 the metallated carbon atoms display a markedly carbenic character and that in solution these species exist at room temperature solely as the ring-closed products, without any observable equilibration to the acyclic isomers. Contrastingly, alkyl reagent 1 decreases the magnesiation rate of btz facilitating an intriguing new cascade activation process of two molecules of substrate involving a sequence of deprotonation/coordination/C-C coupling and ring-opening reactions to yield [{Ar*NC(Me)CHC(Me)NAr*}Mg{(btz*)C(H)]=N(o-C6H4) S}] (5). Hydrolysis of 5 followed by addition of the radical oxidant TEMPO ultimately produces the homocoupled product bis(benzothiazole) 6 in a 72% isolated yield. Thus, this establishes a novel transition-metal-free method to prepare homocoupled thiazoles. More straightforwardly, the coordination product [{Ar*NC(Me)CHC(Me)NAr*}Mg(Bu)(blm(Me))] (8) was obtained when equimolar amounts of blm(Me) and 1 were reacted, illustrating the kinetic stubbornness of the Mg-C bond in butyl derivative 1. Complex 8 can be envisaged as a valuable guide to the constitution of a premetallation complex (in relation to the complex-induced proximity effect, CIPE)

A novel method for the Baeyer–Villiger oxidation of ketones has been developed and optimized. The transformation involves a transition metal-free activation of hydrogen peroxide under Payne epoxidation conditions. Reaction of a ketone with hydrogen peroxide in the presence of a nitrile under mildly basic reaction conditions leads to the corresponding ester. The transformation has been successfully applied to a range of ketones in moderate to excellent yields (30–91 and good to excellent regioselectivities (7:1 to 20:1)

The novel method for the Baeyer—Villiger oxidation of ketones involves a transition metal‐free activation of H2O2 under Payne epoxidation conditions.

The catalytic behavior of the applied catalyst can be tuned by controlling the steric bulk of the isocyanates employed.