C-H Amidation and Amination of Arenes and Heteroarenes with Amide and Amine using Cu-MnO as a Reusable Catalyst under Mild Conditions.

An atom-economical and efficient route for the direct amidation and amination of aryl C-H bonds using our synthesized recyclable heterogeneous Cu-MnO catalyst is reported here. The direct C-H amidation was carried out using a simple amide without any preactivated coupling partner, and simple air was used as the sole oxidant. The reaction proceeds very smoothly with a broad range of substrates containing numerous functional groups in very good to excellent yields. Direct C-H aminations with a secondary amine were carried out under base-, ligand-, and external oxidant-free conditions in very good to excellent yields in very mild conditions. Both the amidation and amination can be scaled up on a gram scale with similar yields. The major advantage is that our catalyst is recyclable and reused several times without any significant loss of reactivity.

Hydrogenated MoS2 QD-TiO2 heterojunction mediated efficient solar hydrogen production.

Herein, we report the development of a hydrogenated MoS2 QD-TiO2 (HMT) heterojunction as an efficient photocatalytic system via a one-pot hydrothermal reaction followed by hydrogenation. This synthetic strategy facilitates the formation of MoS2 QDs with an enhanced band gap and a proper heterojunction between them and TiO2, which accelerates charge transfer process. Hydrogenation leads to oxygen vacancies in TiO2, enhancing the visible light absorption capacity through narrowing its band gap, and sulfur vacancies in MoS2, which enhance the active sites for hydrogen adsorption. Due to the band gap reduction of hydrogenated TiO2 and the band gap enhancement of the MoS2 QDs, the energy states are rearranged to create a reverse movement of electrons and holes facilitated the charge transfer process which enhance life-time of photo-generated charges. The photocatalyst showed stable, efficient and exceptionally high noble metal free sunlight-induced hydrogen production with a maximum rate of 3.1 mmol g-1 h-1. The developed synthetic strategy also provides flexibility towards the shape of the MoS2, e.g. QDs/single or few layers, on TiO2 and offers the opportunity to design novel visible light active photocatalysts for different applications.

Atmospheric pressure aminocarbonylation of aryl iodides using palladium nanoparticles supported on MOF-5.

An efficient amide synthesis by atmospheric pressure aminocarbonylation using palladium nanoparticles supported on MOF-5 is reported. Interestingly, only 0.5 wt% palladium loading was required to achieve high yields. The catalyst is recyclable and offers negligible palladium leaching.

Synthesis of all stereoisomers of KRN7000, the CD1d-binding NKT cell ligand.

KRN7000 is an important ligand identified for CD1d protein of APC, and KRN7000/CD1d complex can stimulate NKT cells to release Th1 and Th2 cytokines. In an effort to understand the structure-activity relationships, we have carried out the synthesis of a complete set of the eight KRN7000 stereoisomers, and their biological activities have been examined.

Chemistry of enediynyl azides: activation through a novel pathway.

The spontaneous activation of a nonaromatic enediynyl azide under ambient conditions has been demonstrated. The aromatic enediyne followed the expected cycloaddition with the alkene in the neighbouring arm to form a stable bridged bicyclic enediyne.

A novel azetidinyl gamma-lactam based peptide with a preference for beta-turn conformation.

Novel azetidinyl gamma-lactam based peptides have been synthesized with only compound showing a preference for the beta-turn conformation.