In Situ Generated Ag(II)-Catalyzed Selective Oxo-Esterification of Alkyne with Alcohol to α-Ketoester: Photophysical Study.

An expert and easy one-step catalytic method for the multi O-C coupling of alkyne is developed for the synthesis of valuable α-ketoesters and their chiral analogues, in contrast to the generation of esters by a noncatalytic method. The in situ generated powerful Ag(II) catalyst from AgOTf is the workhorse in the oxidative grafting of alkyne with PhIO and alcohol. The radical mechanism is confirmed in our controlled experiments and UV-vis study.

PdII-Catalyzed Oxidative Aldehyde-sp2C-H Functionalization and Cyclization Using NHC with Mild Oxidant DMSO for the Selective Synthesis of Esters, Sugar-Based Analogues, and ß-Hydroxy Chromanones: An 18O-Labeling Study.

We assume formation of acyl-PdII-N-heterocyclic-carbene (NHC) organometalics for diverse C-O/O-C and C-C/C-O coupling catalysis of direct functionalization and cyclization reactions. We report the first use of dimethyl sulfoxide (DMSO) as an oxidant under an inert atmosphere to O2-sensitive NHC for oxidative transformations. In situ generated imidazolium halides are utilized as a precursor of NHC and as a source of alkyl group for the sp2C-H functionalization of aldehydes to esters under mild conditions. In contrast to the reported NHC-catalyzed esterification strategies, the outstanding substrate scope of this mild catalysis approach is established through synthesis of thermally labile sugar-based chiral esters. Our competition experiments using various unsymmetrical imidazolium halides revealed an ascending rate of migratory aptitude among methyl ≪ allyl < crotyl < cinnamyl < benzyl moiety. DMSO is used as an oxidant for both esterification and cyclization reactions, and the transfer of the DMSO-oxygen to ester is confirmed using an 18O-labeling experiment. The diverse activity using DMSO-oxygen to acyl-PdII-NHC is verified by developing a unique C-C-coupled cyclization with side-chain hydroxylation of olefin to achieve valuable ß-hydroxy chromanones.

Functionalised Mn(VI)-nanoparticles: an advanced high-valent magnetic catalyst.

We discover Mn(VI)-nanoparticles (NPs) bearing functional groups, high oxidation state, strong electron affinity, unique redox and paramagnetic nature, which opens up a new avenue to catalysis, magnetism and material application. However, its synthesis is challenging and remains unexplored because of associated serious difficulties. A simple benign synthetic strategy is devised to fabricate the high-valent NPs using mild reducing agent bromide, which transformed Mn(VII) to valuable Mn(VI)-species. The EELS-imaging of individual elements, ESI-MS, XPS and other techniques established its composition as Br(Me3SiO)Mn(VI)O2. It revealed significantly improved magnetic moment (SQUID) with isotropic hyperfine splitting of six line spectrum (EPR). The high-oxidation state and incorporated-ligands of the metals present on the active surface of the NPs led to development of a general catalytic process for oxidative heterodifunctionalisation to C-C triple bond towards formation of a new O-C/N-C/S-C and C-C coupling cum cyclisation to biologically important flavones and their aza- and marcapto-analogues, and valuable enaloxy synthons.