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1. gem-Difluoroallylation of Aryl Halides and Pseudo Halides with Difluoroallylboron Reagents in High Regioselectivity

   https://doi.org/10.1002/anie.202111476  

   Sakamoto, Shu; Butcher, Trevor W.; Yang, Jonathan L.; Hartwig, John F. (October 2021, Angewandte Chemie)

   We report the palladium-catalyzed gem-difluoroallylation of aryl halides and pseudo halides with 3,3-difluoroallyl boronates in high yield with high regioselectivity, and we report the preparation of the 3,3-difluoroallyl boronate reactants by a copper-catalyzed defluorinative borylation of inexpensive gaseous 3,3,3-trifluoropropene with bis(pinacola-to) diboron. The gem-difluoroallylation of aryl and heteroaryl bromides proceeds with low catalyst loading (0.1 mol% [Pd]) and tolerates a wide range of functional groups, including primary alcohols, secondary amines, ethers, ketones, esters, amides, aldehydes, nitriles, halides, and nitro groups. This protocol extends to aryl iodides, chlorides, and triflates, as well as substituted difluoroallyl boronates, providing a versatile synthesis of gem-difluoroallyl arenes that we show to be valuable intermediates to a series of fluorinated building blocks 

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2. Fe-catalyzed three-component dicarbofunctionalization of unactivated alkenes with alkyl halides and Grignard reagents

   https://doi.org/10.1039/D0SC02127J  

   Liu, Lei; Lee, Wes; Youshaw, Cassandra R.; Yuan, Mingbin; Geherty, Michael B.; Zavalij, Peter Y.; Gutierrez, Osvaldo (August 2020, Chemical Science)

   null (Ed.)

   A highly chemoselective iron-catalyzed three-component dicarbofunctionalization of unactivated olefins with alkyl halides (iodides and bromides) and sp 2 -hybridized Grignard reagents is reported. The reaction operates under fast turnover frequency and tolerates a diverse range of sp 2 -hybridized nucleophiles (electron-rich and electron-deficient (hetero)aryl and alkenyl Grignard reagents), alkyl halides (tertiary alkyl iodides/bromides and perfluorinated bromides), and unactivated olefins bearing diverse functional groups including tethered alkenes, ethers, protected alcohols, aldehydes, and amines to yield the desired 1,2-alkylarylated products with high regiocontrol. Further, we demonstrate that this protocol is amenable for the synthesis of new (hetero)carbocycles including tetrahydrofurans and pyrrolidines via a three-component radical cascade cyclization/arylation that forges three new C–C bonds. 

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3. Scalable, Chemoselective Nickel Electrocatalytic Sulfinylation of Aryl Halides with SO ₂

   https://doi.org/10.1002/anie.202208080  

   Lou, Terry Shing‐Bong; Kawamata, Yu; Ewing, Tamara; Correa‐Otero, Guillermo A.; Collins, Michael R.; Baran, Phil S. (August 2022, Angewandte Chemie International Edition)

   Abstract Simple access to aryl sulfinates from aryl iodides and bromides is reported using an inexpensive Ni‐electrocatalytic protocol. The reaction exhibits a broad scope, uses stock solution of simple SO₂as sulfur source, and can be scaled up in batch and recycle flow settings. The limitations of this reaction are clearly shown and put into context by benchmarking with state‐of‐the‐art Pd‐based methods. 

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4. Photochemically Driven Nickel‐Catalyzed Carboxylative C−N Coupling: Scope and Mechanism

   https://doi.org/10.1002/chem.202301271  

   Abid, Seifallah; Quirion, Kevin P.; Yang, Yi; Tang, Renhe; Mai, Binh Khanh; Liu, Peng; Tlili, Anis (August 2023, Chemistry – A European Journal)

   Herein we disclosed an unprecedented photochemically driven nickel‐catalyzed carboxylative Buchwald–Hartwig amination to access a wide range of aryl carbamate derivatives. This reaction is performed under mild condition of temperature and atmospheric pressure of CO2 starting from commercially available (hetero)aryl iodides/bromides derivatives and alkyl amines preventing the formation of hazardous and/or toxic waste. Moreover, preliminary mechanistic investigations including stochiometric experiments as well as DFT calculations allow us to shed light on the reaction mechanism. 

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5. Synthesis of conjugated polymers using aryl-bromides via Cu-catalyzed direct arylation polymerization (Cu-DArP)

   https://doi.org/10.1039/c9py01478k  

   Ye, Liwei; Pankow, Robert M.; Schmitt, Alexander; Thompson, Barry C. (December 2019, Polymer Chemistry)

   Initial reports on the novel Cu-catalyzed direct arylation polymerization (Cu-DArP) stated that it required the use of aryl iodides. Herein, we report the first Cu-DArP methodology using more accessible and practical aryl-bromides with catalytic Cu, leading to a range of conjugated polymers with good molecular weights (up to 17.3 kDa) and an undetectable level of defects. 

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