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An α‐difluoroalkylation of benzyl amines with trifluoromethylarenes is disclosed herein. This protocol is characterized by its operational simplicity, excellent chemoselectivity and broad scope—even with advanced synthetic intermediates—, thus offering a new entry point to medicinally‐relevant α‐difluoroalkylated amines from simple, yet readily accessible, precursors. [ABSTRACT FROM AUTHOR]

Herein, we report a Cu‐mediated trifluoromethylation of carbonyl‐type compounds and unactivated olefins enabled by visible‐light irradiation via σ C(sp3)−C bond‐functionalization. The reaction is distinguished by its modularity, mild conditions and wide scope—even in the context of late‐stage functionalization—thus offering a complementary approach en route to valuable C(sp3)−CF3 architectures from easily accessible precursors. [ABSTRACT FROM AUTHOR]

Herein, we describe a Pd-catalyzed arylation of 1,2-amino alcohols with aryl halides enabled by a retroallylation manifold. This protocol constitutes a new entry point to β-arylated aldehydes via the intermediacy of in situ generated enamine intermediates. The protocol is characterized by its exquisite regioselectivity profile and broad substrate scope – including challenging substrate combinations – even in an enantioselective manner. [ABSTRACT FROM AUTHOR]

The ability to selectively forge C–heteroatom bonds by C−F scission is typically accomplished by metal catalysts, specialized ligands and/or harsh reaction conditions. Described herein is a base‐mediated defluorosilylation of unactivated C(sp2)−F and C(sp3)−F bonds that obviates the need for metal catalysts. This protocol is characterized by its simplicity, mild reaction conditions, and wide scope, even within the context of late‐stage functionalization, constituting a complementary approach to existing C−Si bond‐forming protocols. Base motive: A base‐promoted defluorosilylation of unactivated C(sp2)−F and C(sp3)−F bonds, obviating the need for transition‐metal catalysis, specialized ligands, or harsh reaction conditions, has been developed. The salient features of this method are the mild reaction conditions, ease of execution, and wide substrate scope, even within the context of late‐stage functionalization of advanced fluorinated building blocks, thus offering a complementary reactivity mode to existing silylation technologies. [ABSTRACT FROM AUTHOR]

The natural occurrence of amides and their unique roles in synthetic materials and biologically active compounds make amide synthesis one of the most routinely performed reactions in organic chemistry. Despite the advances achieved, there is a growing need for the design of new catalytic technologies to complement existing amide bond‐forming reactions, which are often based on the formation of carbon–nitrogen bonds. Recent years have witnessed the development of a new disconnection approach to forging amides by means of metal‐catalyzed carbon–carbon bond‐forming reactions. This microreview highlights the most recent developments in the use of isocyanates in metal‐catalyzed amidations that take place according to this design principle. With the aim of illustrating the prospective impact of the use of isocyanates as amide synthons, this review highlights the advantages and drawbacks of the existing methods and describes the mechanistic implications when appropriate. [ABSTRACT FROM AUTHOR]

Abstract: A nickel‐catalyzed reductive arylation of ambiphilic α‐bromoalkyl boronic esters with aryl halides is described. This platform provides an unrecognized opportunity to promote the catalytic umpolung reactivity of ambiphilic reagents with aryl halides, thus unlocking a new cross‐coupling strategy that complements existing methods for the preparation of densely functionalized alkyl‐substituted organometallic reagents from simple and readily accessible precursors. [ABSTRACT FROM AUTHOR]

A switchable site-selective catalytic carboxylation of allylic alcohols has been developed in which CO2 is used with dual roles, both facilitating C−OH cleavage and as a C1 source. This protocol is characterized by its mild reaction conditions, absence of stoichiometric amounts of organometallic reagents, broad scope, and exquisite regiodivergency which can be modulated by the type of ligand employed. [ABSTRACT FROM AUTHOR]

A user-friendly, nickel-catalyzed reductive amidation of unactivated primary, secondary, and tertiary alkyl bromides with isocyanates is described. This catalytic strategy offers an efficient synthesis of a wide range of aliphatic amides under mild conditions and with an excellent chemoselectivity profile while avoiding the use of stoichiometric and sensitive organometallic reagents. [ABSTRACT FROM AUTHOR]

A nickel-catalyzed reductive carboxylation technique for the synthesis of cyclopropanecarboxylic acids has been developed. This user-friendly and mild transformation operates at atmospheric pressure of carbon dioxide and utilizes either organic halides or alkene precursors, thus representing the first example of catalytic reductive carboxylation of secondary counterparts lacking adjacent π-components. [ABSTRACT FROM AUTHOR]

The ability of nickel to cleave strong σ‐bonds is again in the spotlight after a recent report that demonstrates the feasibility of using nickel complexes to promote decarbonylation of diaryl ketones. This transformation involves the cleavage of two strong C−C(O) bonds and avoids the use of noble metals, hence reinforcing the potential of decarbonylation as a technique for forging C−C bonds. [ABSTRACT FROM AUTHOR]

The back cover of the journal "Angewandte Chemie International Edition" is presented.

A switchable site-selective catalytic carboxylation of allylic alcohols has been developed in which CO2 is used with dual roles, both facilitating C−OH cleavage and as a C1 source. This protocol is characterized by its mild reaction conditions, absence of stoichiometric amounts of organometallic reagents, broad scope, and exquisite regiodivergency which can be modulated by the type of ligand employed. [ABSTRACT FROM AUTHOR]