A green approach for the synthesis of thermodynamically less stable Z-alkenes has been presented through the exploration of visible light promoted photocatalytic E-to-Z isomerization. This protocol features metal-free conditions, which is operationally simple, remarkably clean, and allows the synthesis of both electron-rich and electron-deficient Z-alkenes with diverse functional groups.

A distinctive visible light-promoted photocatalytic approach for the C–H silylation of heteroarenes by using trialkylhydrosilanes was developed.

An efficient Lewis acid‐catalyzed C(sp3)–C(sp3) bond forming annulation reaction has been developed. This strategy serves as a new method for the facile synthesis of tetrahydro‐5H‐isoquinolino[2,1‐g][1,6]naphthyridine derivatives. A wide range of 2‐methylquinoline‐3‐carbaldehydes and 1,2,3,4‐tetrahydroisoquinolines can be applied for this process to afford structurally diverse tetrahydroprotoberberine derivatives in excellent yields.magnified image

A hypervalent iodine­(III)-mediated intramolecular decarboxylative Heck-type reaction of 2-vinyl-phenyl oxamic acids has been developed. The unique ring-strain-enabled radical decarboxylation mechanism is preliminarily revealed. This protocol features metal-free reaction conditions and operational simplicity, allowing the lactamization of 2-vinylanilines using a readily accessible carbonyl source and the synthesis of various 2-quinolinones with excellent chemoselectivity at room temperature.

An unprecedented tandem N-alkylation-ionic aza-Cope (or Claisen) rearrangement-hydrolysis reaction of readily available indolyl bromides with enamines is described. Due to the complicated nature of the two processes, an operationally simple N-alkylation and subsequent microwave-irradiated ionic aza-Cope rearrangement-hydrolysis process has been uncovered. The tandem reaction serves as a powerful approach to the preparation of synthetically and biologically important, but challenging, 2-reverse quaternary-centered prenylated indoles with high efficiency. Notably, unusual nonaromatic 3-methylene-2,3-dihydro-1H-indole architectures, instead of aromatic indoles, are produced. Furthermore, the aza-Cope rearrangement reaction proceeds highly regioselectively to give the quaternary-centered reverse prenyl functionality, which often produces a mixture of two regioisomers by reported methods. The synthetic value of the resulting nonaromatic 3-methylene-2,3-dihydro-1H-indole architectures has been demonstrated as versatile building blocks in the efficient synthesis of structurally diverse 2-reverse prenylated indoles, such as indolines, indole-fused sultams and lactams, and the natural product bruceolline D.