Anomeric Amide-Enabled Alkene-Arene and Alkene-Alkene Aminative Coupling.

Despite the prominence of C-N bond forming cross-coupling reactions as a strategy to assemble molecular fragments, aminative coupling approaches, in which two fragments are assembled directly at the heteroatom, represents a rarely exploited retrosynthetic strategy. Herein, we report the design, synthesis, and implementation of an anomeric amide reagent capable of promoting highly regioselective aminative alkene-arene and alkene-alkene coupling reactions. This transformation follows a sequence of catalyst-free chloroamination, N-deprotection, and formal nitrene functionalization, all in one-pot.

Nitrogen-to-functionalized carbon atom transmutation of pyridine.

The targeted and selective replacement of a single atom in an aromatic system represents a powerful strategy for the rapid interconversion of molecular scaffolds. Herein, we report a pyridine-to-benzene transformation nitrogen-to-carbon skeletal editing. This approach proceeds a sequence of pyridine ring-opening, imine hydrolysis, olefination, electrocyclization, and aromatization to achieve the desired transmutation.

Bicyclo[1.1.0]butyl Radical Cations: Synthesis and Application to [2π + 2σ] Cycloaddition Reactions.

As the chemistry that surrounds the field of strained hydrocarbons, such as bicyclo[1.1.0]butane, continues to expand, it becomes increasingly advantageous to develop alternative reactivity modes that harness their unique properties to access new regions of chemical space.

A focus on sustainable method development for greener synthesis.

Given the current global climate and health challenges, sustainability and cost-effectiveness are becoming unavoidable factors that must be considered in the development of new synthetic methodologies. In a recent publication, Kavthe (R. D.

Four-Component Strain-Release-Driven Synthesis of Functionalized Azetidines.

Despite the favorable properties that azetidine rings can engender on drug-compounds, methods for the diversity-oriented synthesis of azetidine-based structures are significantly underdeveloped. Herein, we report the successful realization of a multicomponent [1,2]-Brook rearrangement/strain-release-driven anion relay sequence and its application to the modular synthesis of substituted azetidines. The rapidity of the reaction, as confirmed by in situ infra-red spectroscopy, leverages the strain-release ring-opening of azabicyclo[1.

Strain-Release-Driven Friedel-Crafts Spirocyclization of Azabicyclo[1.1.0]butanes.

The identification of spiro N-heterocycles as scaffolds that display structural novelty, three-dimensionality, beneficial physicochemical properties, and enable the controlled spatial disposition of substituents has led to a surge of interest in utilizing these compounds in drug discovery programs. Herein, we report the strain-release-driven Friedel-Crafts spirocyclization of azabicyclo[1.1.

Strain-Release Driven Spirocyclization of Azabicyclo[1.1.0]butyl Ketones.

Due to their intrinsic rigidity, three-dimensionality and structural novelty, spirocyclic molecules have become increasingly sought-after moieties in drug discovery. Herein, we report a strain-release driven synthesis of azetidine-containing spirocycles by harnessing the inherent ring strain of the azabicyclo[1.1.