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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., (© 2024 Wiley-VCH GmbH.)

Herein, we disclose a new strategy that rapidly and reliably incorporates bromine atoms at distal, secondary C(sp 3 )-H sites in aliphatic amines with an excellent and predictable site-selectivity pattern. The resulting halogenated building blocks serve as versatile linchpins to enable a series of carbon-carbon and carbon-heteroatom bond-formations at remote C(sp 3 ) sites, thus offering a new modular and unified platform that expediates the access to advanced sp 3 architectures possessing valuable nitrogen-containing saturated heterocycles of interest in medicinal chemistry settings., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

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., (© 2023 Wiley-VCH GmbH.)

Herein, we describe a catalytic intramolecular decarboxylative/desulfonylative sp 3 allylation triggered by sulfinate salts under light irradiation. The reaction is likely enabled by a non-classical, radical-polar crossover mechanism, allowing rapid and reliable access to valuable allyl architectures from readily accessible precursors. The protocol is characterized by its operational simplicity and scalability, employing abundant, commercially available catalysts., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Herein, we report a Cu-mediated trifluoromethylation of carbonyl-type compounds and unactivated olefins enabled by visible-light irradiation via σ C(sp 3 )-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(sp 3 )-CF 3 architectures from easily accessible precursors., (© 2022 Wiley-VCH GmbH.)

Herein, we describe the development of a copper-catalyzed C(sp 3 )-amination of proaromatic dihydroquinazolinones derived from ketones. The reaction is enabled by the intermediacy of open-shell species arising from homolytic C-C bond-cleavage driven by aromatization. The protocol is characterized by its operational simplicity and generality, including chemical diversification of advanced intermediates., (© 2022 Wiley-VCH GmbH.)

A nickel-catalyzed site-selective intermolecular amidation of saturated C(sp 3 )-H bonds is reported. This mild protocol exhibits a predictable reactivity pattern to incorporate amide functions at C(sp 3 )-H sites adjacent to nitrogen and oxygen atoms in either cyclic or acyclic frameworks, thus offering a complementary reactivity profile to existing oxidative-type processes or metal-catalyzed C(sp 3 )-N bond-forming reactions operating via two-electron manifolds., (© 2022 Wiley-VCH GmbH.)

A catalytic 1,1-difunctionalization of unactivated olefins en route to sp 3 bis-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 sp 3 bis-organometallics., (© 2021 Wiley-VCH GmbH.)

A modular, site-selective 1,2-dicarbofunctionalization of vinyl boronates with organic halides through dual catalysis is described. This reaction proceeds under mild conditions and is characterized by excellent chemo- and regioselectivity. It thus represents a complementary new technique for preparing densely functionalized alkyl boron architectures from simple and accessible precursors., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A base-catalyzed reaction that enables stereoselective 1,1-silaboration of terminal alkynes is described. This method not only offers a new strategy to functionalize simple and readily accessible alkynes beyond 1,2-difunctionalization, but also provides an unconventional atom- and step-economical approach to rapidly and reliably access versatile geminal silylboranes in the absence of transition metals and with exquisite stereoselectivity., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A photoinduced carboxylation of alkyl halides with CO 2 at remote sp 3 C-H sites enabled by the merger of photoredox and Ni catalysis is described. This protocol features a predictable reactivity and site selectivity that can be modulated by the ligand backbone. Preliminary studies reinforce a rationale based on a dynamic displacement of the catalyst throughout the alkyl side chain., (© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

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(sp 2 )-F and C(sp 3 )-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., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Driven by the inherent synthetic potential of CO 2 as an abundant, inexpensive and renewable C 1 chemical feedstock, the recent years have witnessed renewed interest in devising catalytic CO 2 fixations into organic matter. Although the formation of C-C bonds via catalytic CO 2 fixation remained rather limited for a long period of time, a close look into the recent literature data indicates that catalytic carboxylation reactions have entered a new era of exponential growth, evolving into a mature discipline that allows for streamlining the synthesis of carboxylic acids, building blocks of utmost relevance in industrial endeavors. These strategies have generally proven broadly applicability and convenient to perform. However, substantial challenges still need to be addressed reinforcing the need to cover metal-catalyzed carboxylation area in a conceptual and concise manner, delineating the underlying new principles that are slowly emerging in this vibrant area of expertise., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A redox-neutral intermolecular dicarbofunctionalization of styrenes with CO 2 at atmospheric pressure and carbon-centered radicals is described. This mild protocol results in multiple C-C bond-forming reactions from simple precursors in the absence of stoichiometric reductants, thus exploiting a previously unrecognized opportunity that complements existing catalytic carboxylation events., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A switchable site-selective catalytic carboxylation of allylic alcohols has been developed in which CO 2 is used with dual roles, both facilitating C-OH cleavage and as a C 1 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., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A user-friendly Ni-catalyzed reductive carboxylation of benzylic C-N bonds with CO2 is described. This procedure outperforms state-of-the-art techniques for the carboxylation of benzyl electrophiles by avoiding commonly observed parasitic pathways, such as homodimerization or β-hydride elimination, thus leading to new knowledge in cross-electrophile reactions., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The first catalytic intermolecular proximal C1-C2 cleavage of benzocyclobutenones (BCB) without prior carbonyl activation or employing noble metals has been developed. This protocol operates at room temperature and is characterized by an exquisite chemo-, regio- and diastereoselectivity profile, constituting a unique platform for preparing an array of elusive carbocyclic skeletons., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We report the first enantioselective CC bond formation through CO bond cleavage using aryl ester counterparts. This method is characterized by its wide substrate scope and results in the formation of quaternary stereogenic centers with high yields and asymmetric induction., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A tandem C(sp(2))-H and C(sp(3))-H functionalization/C-O bond formation catalyzed by iodine(III) reagents generated in situ has been developed. The method shows wide scope under mild conditions and exhibits an unprecedented selectivity profile that can be switched depending on the catalyst employed., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Metal-catalyzed reductive coupling reactions of aryl halides and (pseudo)halides with carbonyl-type compounds have undergone an impressive development within the last years. These methodologies have shown to be a powerful alternate strategy, practicality aside, to the use of stoichiometric, well-defined, and, in some cases, air-sensitive organometallic species. In this Minireview, the recent findings in this field are summarized, with particular emphasis on the mechanistic interpretation of the results and future aspects of this area of expertise., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)