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Herein, we report a modular catalytic technique that streamlines the preparation of gem -difluoroalkanes from unactivated sp 3 precursors. The method is characterized by its simplicity, generality, and site selectivity, including the functionalization of advanced intermediates and olefin feedstocks. Our approach is enabled by a cooperative interplay of halogen- and hydrogen-atom transfer, thus offering a new entry point to difluorinated alkyl bioisosteres of interest in drug discovery.

Herein, we report the first Ni-catalyzed enantioselective deaminative alkylation of amino acid and peptide derivatives with unactivated olefins. Key for success was the discovery of a new sterically encumbered bis(oxazoline) ligand backbone, thus offering a de novo technology for accessing enantioenriched sp 3 - sp 3 linkages via sp 3 C-N functionalization. Our protocol is distinguished by its broad scope and generality across a wide number of counterparts, even in the context of late-stage functionalization. In addition, an enantioselective deaminative remote hydroalkylation reaction of unactivated internal olefins is within reach, thus providing a useful entry point for forging enantioenriched sp 3 - sp 3 centers at remote sp 3 C-H sites.

A tungsten-catalyzed hydroboration of unactivated alkenes at distal C(sp 3 )-H bonds aided by native directing groups is described herein. The method is characterized by its simplicity, exquisite regio- and chemoselectivity, and wide substrate scope, offering a complementary site-selectivity pattern to other metal-catalyzed borylation reactions and chain-walking protocols.

Herein, we describe a stereoselective Ni‐catalyzed N‐glycosylation of glycals. The reaction is enabled by addition of an in situ generated nickel hydride across an olefin prior to C−N bond‐formation. Stereodivergence can be accomplished on kinetic or thermodynamic grounds, thus giving access to either α‐ or β‐N‐glycosides with equal ease. The protocol is distinguished by its operational simplicity, generality and exquisite selectivity, thus offering a new gateway to expedite the synthesis of N‐glycosides. [ABSTRACT FROM AUTHOR]

Unactivated olefins rank amongst the most important feedstocks in organic synthesis. Their availability makes them particularly useful synthons for subsequent functionalization, particularly in a catalytic manner. Driven by the popularity ascribed by nickel catalysis as a new tool to rapidly forge molecular architectures via one‐or two‐electron manifolds, the recent years have witnessed significant advances in Ni‐catalyzed olefin difunctionalization. While 1,2‐difunctionalization or remote functionalization via "chain‐walk" have become mature disciplines for repurposing the potential of olefins as building blocks, it was only recently that extensions of this chemistry to 1,1‐difunctionalization have been possible. This review summarizes the recent advances in Ni‐catalyzed olefin 1,1‐difunctionalization, holding considerable promise as a new powerful strategy for our ever‐growing synthetic repertoire. [ABSTRACT FROM AUTHOR]

A dual photocatalytic sulfonylation‐arylation of electron‐rich alkenes is described. By combining sulfinate salts, (hetero)‐aryl‐bromides and 2,3‐dihydrofuran under Ru and Ni dual catalysis, over 35 examples of aryl‐sulfonylated scaffolds could be obtained in good to excellent yields, under mild reaction conditions and high diastereoselectivity. [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]

A catalytic 1,1‐difunctionalization of unactivated olefins en route to sp3bis‐organometallic B,B(Si)‐reagents is described. The protocol is characterized by exceptional reaction rates, mild conditions, wide scope, and exquisite selectivity pattern, constituting a new platform to access sp3bis‐organometallics. [ABSTRACT FROM AUTHOR]

A carboacylation of iodoalkyl olefins with carbon monoxide provides 5- to 7-membered cyclic compounds under mild reaction conditions. [ABSTRACT FROM AUTHOR]

This article focuses on the iron (Fe)-catalyzed cross-coupling reactions of organomagnesium reagents with various electrophiles, which were guided by the hypothesis that bare, low-valent iron clusters formed in situ from Fe and excess magnesium. Since the unambiguous characterization of such highly reactive species is problematic, the ongoing mechanistic studies rely on the use of the Fe complexes as adequate surrogates. These structurally well-defined compounds comprise very electron-rich metal centers within a coordination sphere of weakly bound alkene ligands.