A novel and expedient cascade strategy has been demonstrated for the synthesis of fused benzo‐aza‐oxa‐[5‐6‐5] tetracycles in high yields and diastereoselectivities (up to 20 : 1 dr). The strategy was fulfilled through palladium‐catalyzed oxidative convergent assembly of functionally divergent anilines and 3‐butenoic acid with five chemical bonds constructed. Coupled with control experiments and deuterium labelled studies, DFT calculations were performed for the proposed mechanism. The utility of the illustrated strategy is emphasized by gram‐scale syntheses, late‐stage functionalization, and the transformation to a key core of natural products such as martinellic acid and seneciobipyrrolidine.

Thea ssembly of two functional molecules via asulfurlinking atom allowsanaccess to adiverse array of thioether-containing compounds.H erein, we disclose am etal-free thiolation of imidazopyridines with av ariety of functionalized haloalkanes using elemental sulfur.

An efficient method for the synthesis of (E)-β-aryl sulfonyl acrylates has been reported. This palladium-catalyzed approach showed excellent regio-and stereoselectivity in the sulfonylation of aryl propiolates with sulfonyl hydrazides. Through this approach, a wide range of (E)-β-aryl sulfonyl acrylates were obtained in moderate to high yields. Scheme 3. Substrate scope of sulfonyl hydrazides. [a] Scheme 4. Mechanistic studies. Scheme 5. Plausible mechanism.

A novel palladium-catalyzed amination and nitration of ethyl vinyl ether for the construction of β-nitroamine derivatives under mild conditions has been developed. This transformation provides a new strategy for the installation of amino and nitro from aromatic amines and nitro-paraffin into alkenes. Morpholine resulted in the aza-Henry reaction, while DABCO led to the unexpected rearrangement.

A novel and expedient cascade strategy has been demonstrated for the synthesis of fused benzo-azaoxa- [5-6-5] tetracycles in high yields and diastereoselectivities (up to 20 : 1 dr). The strategy was fulfilled through palladium-catalyzed oxidative convergent assembly of functionally divergent anilines and 3-butenoic acid with five chemical bonds constructed. Coupled with control experiments and deuterium labelled studies, DFT calculations were performed for the proposed mechanism. The utility of the illustrated strategy is emphasized by gram-scale syntheses, late-stage functionalization, and the transformation to a key core of natural products such as martinellic acid and seneciobipyrrolidine.