Photoredox-Catalyzed Strain-Release-Driven Synthesis of Functionalized Spirocyclobutyl Oxindoles.

Spirocyclobutyl oxindoles have garnered substantial attention in drug discovery and pharmaceuticals owing to their wide range of biological activities. Strain-release in small-ring compounds is a powerful strategy to enable efficient access to complex molecules. In this study, we successfully realized a photoredox-catalyzed strain-release radical spirocyclization approach to attain functionalized spirocyclobutyl oxindoles.

Strain-enabled radical spirocyclization cascades: rapid access to spirocyclobutyl lactones and - lactams.

Spirocyclobutane derivatives have gained significant attention in drug discovery programs due to their broad spectrum of biological activities and clinical applications. Ring-strain in organic molecules is a powerful tool to promote reactivity by releasing strain energy, allowing the construction of complex molecules selectively and efficiently. Herein, we report the first strain-enabled radical spirocyclization cascades for the synthesis of functionalized spirocyclobutyl lactones and - lactams, which are finding increasing applications in medicinal chemistry.

A highly diastereoselective strain-release Doyle-Kirmse reaction: access to functionalized difluoro(methylene)cyclopropanes.

Difluoro(methylene)cyclopropanes (F2MCPs) show better anti-cancer properties and chemical reactivities compared to their nonfluorinated analogues. However, catalytic stereoselective methods to access these privileged motifs still remain a challenging goal. The Doyle-Kirmse reaction is a powerful strategy for the concomitant formation of carbon-carbon and carbon-sulfur bonds.

Assessing inequalities in publicly funded health insurance scheme coverage and out-of-pocket expenditure for hospitalization: findings from a household survey in Kerala.

Background: Increasing financial risk protection is a key feature of Universal Health Coverage and the path towards health for all. Publicly Funded Health Insurance Schemes (PFHIS) have been considered as one of the pathways to safeguard against financial shocks and potentially reduce Out-of-Pocket Expenditure (OOPE). The south Indian state of Kerala has roughly a decade-long experience in implementing PFHIS.

Photocatalyzed Dowd-Beckwith radical-polar crossover reaction for the synthesis of medium-sized carbocyclic compounds.

The Dowd-Beckwith reaction, a ring-expansion of carbonyl compounds alkoxy radicals, is a powerful approach for synthesizing medium to large-sized carbocyclic scaffolds, which takes advantage of existing ring structures and avoids entropic and enthalpic factors that arise from the end-to-end cyclization strategies. However, the Dowd-Beckwith ring-expansion followed by H-atom abstraction is still the dominating pathway, which hampers its synthetic applications, and there currently exist no reports on the functionalization of ring-expanded radicals using non-carbon based nucleophilic reagents. Herein, we report a redox-neutral decarboxylative Dowd-Beckwith/radical-polar crossover (RPC) sequence that delivers functionalized medium-sized carbocyclic compounds with broad functional group tolerance.