Stereoselective Synthesis of Glycosides via Tsuji-Trost Type Glycosylation Using 3,4-Carbonate Galactals.

Pd-catalyzed stereoselective glycosylations using unsaturated sugar derivatives, glycals, have been successfully achieved in recent years. This review focuses on approaches to control the stereoselectivities of glycosides via π-allyl intermediates that mimic the Tsuji-Trost asymmetric allylic alkylation reactions, enabling stereoselectivity control through rational design. In the reaction process, zwitterionic Pd-π-allyl complexes, formed after the oxidative addition and decarboxylation, play a crucial role in increasing reactivities and enhancing the stereoselectivities of α- and β-glycosides.

TRPC4 deletion elicits behavioral defects in sociability by dysregulating expression of microRNA-138-2.

To investigate whether the defects in transient receptor potential canonical 4 (TRPC4), which is strongly expressed in the hippocampus, are implicated in ASD, we examined the social behaviors of mice in which was deleted (). mice displayed the core symptoms of ASD, namely, social disability and repetitive behaviors. In microarray analysis of the hippocampus, microRNA (miR)-138-2, the precursor of miR-138, was upregulated in mice.

Rh(II)-Catalyzed C-N Bond Formation Using Enynones and N-H Imines: An Approach to Diarylmethylamines.

A Rh(II)-catalyzed furyl carbene N-H insertion reaction involving an -sp-hybridized imine is described, which represents an atom-economical route by which to access diarylmethylamine derivatives with high efficiency and broad substrate scope. An unusual reaction mechanism is proposed, in which the rhodium catalyst plays a dual role in facilitating enynone cyclization via activation and enhancement of the nucleophilicity of the NH imine.

Transition Metal-Free, Methoxide-Catalyzed Synthesis of Pyridoindolones.

A simple transition metal-free strategy for the synthesis of pyrido[1,2]indolone derivatives has been devised through sodium methoxide-catalyzed intramolecular cyclization of 2-alkenylated -pyrimidyl indoles. The reactions involved a Smiles rearrangement/cyclization cascade, which resulted in a new series of -fused indoles, potentially applicable skeletons in medicinal chemistry. This reaction presents simple eco-friendly reaction conditions, a high atom- and cost-economy, a short reaction time, and a broad range of substrate scope with high reaction efficiency.

Co-Catalyzed C-H Alkenylation and Allylation with Cyclopropenes via Sequential C-H/C-C Bond Activation.

An atom-economical strategy for the C-H alkenylation and C-H allylation of arenes by employing cyclopropenes as versatile alkenylating and allylating reagents is reported, catalyzed by cobalt. The Co-catalyzed C-H alkenylation process involves sequential C-H and C-C bond cleavage. Under the optimized conditions, broad-ranging alkenylated (hetero)arenes were synthesized with complete ()-stereoselectivity (up to 91%).