Manganese-catalysed divergent silylation of alkenes.

Transition-metal-catalysed, redox-neutral dehydrosilylation of alkenes is a long-standing challenge in organic synthesis, with current methods suffering from low selectivity and narrow scope. In this study, we report a general and simple method for the manganese-catalysed dehydrosilylation and hydrosilylation of alkenes, with Mn(CO) as a catalyst precursor, by using a ligand-tuned metalloradical reactivity strategy. This enables versatility and controllable selectivity with a 1:1 ratio of alkenes and silanes, and the synthetic robustness and practicality of this method are demonstrated using complex alkenes and light olefins.

Selective Hydroarylation of 1,3-Diynes Using a Dimeric Manganese Catalyst: Modular Synthesis of Z-Enynes.

The transition-metal-catalyzed selective hydroarylation of unsymmetrical alkynes represents the state-of-art in organic chemistry, and still mainly relies on the use of precious late-transition-metal catalysts. Reported herein is an unprecedented Mn -catalyzed hydroarylation of unsymmetrical 1,3-diyne alcohols with commercially available arylboronic acids with predictive selectivity. This method addresses the challenges in regio-, stereo-, and chemoselectivity.

Synthesis of cyclohexylidenehydrazine-fused polycyclics via a photocatalytic radical cascade reaction of 2-ethynylaldehyde hydrazones.

A general and efficient visible-light photoredox-catalyzed cascade annulation of 2-ethynylaldehyde hydrazones with α-bromo-carbonyls for the synthesis of various cyclohexylidene-hydrazine-fused polycyclic compounds is described. This protocol is characterized by a broad substrate scope, mild conditions and amenability to gram-scale synthesis.

Metal-Free Radical Oxidative Cyclization of o-Azidoaryl Acetylenic Ketones with Sulfinic Acids To Access Sulfone-Containing 4-Quinolones.

A novel one-pot synthesis of sulfone-containing 4-quinolones with easily available sulfinic acids as sulfonylating precursors is described. This reaction is characterized by mild reaction conditions, high functional-group tolerance and amenability to gram-scale synthesis.

A domino desulfurative coupling-acylation-hydration-Michael addition process for the synthesis of polysubstituted tetrahydro-4H-pyrido[1,2-a]pyrimidines.

A novel method for the synthesis of the polysubstituted tetrahydro-4H-pyrido[1,2-a]pyrimidines through a domino desulfurative coupling-acylation-hydration and Michael addition sequence was established.