A benzimidazole-based Cu(II) complex catalyzed site-selective C-H sulfenylation of imidazo-[1,2-a]pyridines using CS2 as a sulfur source.

A new benzimidazole-based Cu(II) complex catalyzed site-selective sulfenylation of imidazo[1,2-a]pyridines with benzyl/alkyl/allyl bromides and CS2 at 100 °C in DMF : H2O is reported. The present methodology has been developed for the synthesis of 3-sulfenyl imidazo[1,2-a]pyridines in good yields with a broad substrate scope. In this protocol, CS2, commonly known as a non-polar small molecule bioregulator (SMB), is converted to valuable sulfenylated imidazo[1,2-a]pyridine derivatives. In addition, theoretical investigations along with experimental evidence unfold the insights into the probable mechanistic pathway of site-selective sulfenylation from S,S-dibenzyltrithiocarbonate, which is particularly formed as an intermediate during the reaction.

Aerobic Oxidation of Primary Amines to Imines in Water using a Cobalt Complex as Recyclable Catalyst under Mild Conditions.

Oxidative coupling of primary amines to imines has been achieved by using a water soluble cobalt complex as catalyst and air as the oxidant at near ambient conditions. Aromatic, heteroaromatic and aliphatic amines were successfully converted to the corresponding imines with yields of up to 96 %. A 20 gram scale reaction for the synthesis of imine from benzylamine in good yield is also demonstrated with this method. The catalyst has been found to be reusable with up to five cycles. It is highly efficient, gives a turnover number (TON) of up to 128, and shows chemoselectivity with the only byproducts being water and ammonia. Control experiments and mechanistic studies indicate that the CoII /CoIII catalytic cycle is responsible for these oxidative transformations. Some of the reactive intermediates of this reaction have also been isolated and structurally characterized.

Paramagnetic relaxation of long-lived coherences in solution NMR.

Long-lived coherences (LLCs) are known to have lifetimes much longer than transverse magnetization or single quantum coherences (SQCs). The effect of paramagnetic ions on the relaxation of LLCs is not known. This is particularly important, as LLCs have potential applications in various fields like analytical NMR, in vivo NMR and MR imaging methods. We study here the behaviour of LLCs in the presence of paramagnetic relaxation agents. The stepwise increase in the concentration of the metal ion is followed by measuring various relaxation rates. The effect of paramagnetic ions is analysed in terms of the external random field's contribution to the relaxation of two coupled protons in 2,3,6-trichlorobenzaldehyde. The LLCs relax faster than ordinary SQCs in the presence of paramagnetic ions of varying character. This is explained on the basis of an increase in the contribution of the external random field to relaxation due to a paramagnetic relaxation mechanism. Comparison is also made with ordinary Zeeman relaxation rates like R1, R2, R1ρ and also with rate of relaxation of long-lived states RLLS which are known to be less sensitive to paramagnetically induced relaxation. Also, the extent of correlation of random fields at two proton sites is studied and is found to be strongly correlated with each other. The obtained correlation constant is found to be independent of the nature of added paramagnetic impurities.

Synthesis of unsymmetrical multi-aroyl derivatives of ferrocene using palladium catalysed oxidative C-H aroylation.

A palladium catalysed methodology for mono-selective oxidative aroylation of ferrocene has been achieved. 10 mol% of Pd(OAc)2 was used as the catalyst for this radical aroylation reaction using O-methyl-oxime as the directing group. tert-Butyl hydroperoxide was used as an oxidant and both aldehydes and alcohols were used as acyl-equivalents. The protocol has been extended to aryl, heteroaryl and sterically hindered aroylating agents. Acidic-hydrolysis with 6(N) HCl of the directing group resulted in unsymmetrically substituted ketone derivatives of ferrocene, which have not been achieved otherwise.