A convenient, highly efficient, and selective transformation of aliphatic and aromatic carboxylic acids to acyl fluorides is reported. In contrast to established approaches that require toxic or volatile additives and base and reaction control (i.e., cooling, slow addition), this protocol allows for a straightforward access to various R-COF entities upon direct reaction with the bench-stable, solid reagent (MeN)SCF at room temperature. The method is base- and additive-free, compatible with late-stage synthetic applications, high functional group tolerance, and facile target compound purification via filtration.

Reported herein is the one-pot synthesis of trifluoromethylated amines at room temperature using the bench-stable (Me 4 N)SCF 3 reagent and AgF.T he method is rapid, operationally simple and highly selective

Contrary to the general belief that Pd-catalyzed cross-coupling at sites of severe steric hindrance are disfavored, we herein show that the oxidative addition to C À Br ortho to an adamantyl group is as favored as the corresponding adamantyl-free system due to attractive dispersion forces. This enabled the development of a fully selective arylation and alkylation of CÀBr ortho to an adamantyl group, even if challenged with competing non-hindered CÀOTf or CÀCl sites. The method makes use of an air-stable Pd I dimer and enables straightforward access to diversely substituted therapeutically important adamantylarenes in 5-30 min.

While halogenation is of key importance in synthesis and radioimaging,t he currently available repertoire is largely designed to introduce as ingle halogen per molecule.T his report makes the selective introduction of several different halogens accessible.S howcased here is the privileged stability of nontoxicaryl germanes under harsh fluorination conditions (that allows elective fluorination in their presence), while displaying superior reactivity and functional-group tolerance in electrophilic iodinations and brominations,o utcompeting silanes or boronic esters under rapid and additive-free conditions.M echanistic experiments and computational studies suggest ac oncerted electrophilic aromatic substitution as the underlying mechanism.

A highly stereoselective one-pot procedure for the synthesis of five-membered annulated hydroxycoumarins has been developed. By merging primary amine catalysis with silver catalysis, a series of functionalized coumarin derivatives were obtained in good yields (up to 91%) and good to excellent enantioselectivities (up to 99% ee) via a Michael addition/hydroalkoxylation reaction. Depending on the substituents on the enynone, the synthesis of annulated six-membered rings is also feasible.