Radical spirocyclization via dearomatization has emerged as an attractive strategy for the rapid synthesis of structurally diverse spiro molecules. We report the use of electrochemistry to perform an oxidative dearomatization...

Natural allocolchicine and analogues derived thereof a tricyclic 6-7-6-system have been found as key scaffold of various biologically relevant molecules. However, the direct preparation of the allocolchicine motif remains difficult...

During the past few years, electrochemical oxidative reactions through radical intermediates have emerged as an environmentally-benign, powerful platform for the facile formation of C–E (E = C, N, S, Se, O and Hal) bonds through single-electron-transfer (SET) processes at the electrodes. Functionalized unsaturated molecules and unusual structural motifs can, for instance, be directly constructed under exceedingly mild reaction conditions through initial radical attack onto alkynes. This minireview highlights the recent advances in electrooxidation in radical reactions until June 2022, with a particular focus on radical additions onto alkynes.

Dibenzocycloheptanones containing a tricyclic 6–7–6-system are present in numerous biologically active natural molecules.

Radical additions onto olefins have surfaced as an increasingly powerful strategy for the synthesis of difunctionalized scaffolds. However, despite of major advances, known approaches continue to be largely limited to two manifolds, namely 1,2‐difunctionalization of alkenes and remote difunctionalization via hydrogen atom transfer (HAT). Herein, we describe a mechanistically distinct approach by photoinduced carbon‐carbon (C−C) activation/ring‐opening to access γ,δ‐unsaturated aldehydes from methylenecyclobutanols and sulfonyl chlorides by strain release. Remarkably, the sulfonyl motif on the products was easily removed by another photocatalytic process, which enabled the concise assembly of the natural product alatanone A. The synthetic utility of our approach was reflected by versatile functional group tolerance, ample substrate scope, and scalability. The photocatalysis represents a conceptually distinct alternative to existing approaches for remote 1,4‐diversifications, with a double bond remaining in the thus obtained products.