Benchtop Nickel Catalysis Invigorated by Electron-Deficient Diene Ligands

Accounts of Chemical Research, Год журнала: 2024, Номер 57(3), С. 312 - 326

Опубликована: Янв. 18, 2024

ConspectusDue to the rarity of precious metals like palladium, nickel catalysis is becoming an increasingly important player in organic synthesis, especially for formation bonds with sp3-hybridized carbon centers. Traditionally, catalytic processes involving active Ni(0) species have relied on Ni(COD)2 or situ reduction Ni(II) salts. However, air- and temperature-sensitive material that requires use inert-atmosphere glovebox, protocols salts using metallic organometallic reductants add additional complications reaction development.This Account chronicles development air-stable precursors as replacements reduction. Based Schrauzer's seminal discovery Ni(COD)(DQ) zerovalent organonickel complex, our research laboratories at Scripps Research Bristol Myers Squibb developed a class precatalysts based Ni(COD)(EDD) (EDD = electron-deficient diene) framework, relying steric electronic properties supporting diene render metal center stable air, moisture, even silica gel but reactive ligand substitution redox changes.The complexes can be accessed through exchange Ni(COD)2, Ni(acac)2 DIBAL-H, electrochemically via cathodic followed by addition EDD one pot. As toolkit, demonstrate reactivity equivalent enhanced compared catalyzing C–C C–N cross-couplings, Miyaura borylations, C–H activations, other transformations. Since initial report Ni(COD)(DQ), its C(sp2)–CN activation, metallophotoredox, electric field-induced cross-coupling also been demonstrated.By incorporating precatalyst toolkit into campaigns, able perform C(sp3)–S(alkyl) couplings metallonitrenoid carboamination, both which represent challenging transformations were inaccessible traditional phosphine, nitrogen, olefin ligands. Computational experimental studies how quinone ligands are hemilabile, adopting η1(O)-bound geometries relieve strain stabilize transition states intermediates; redox-active, transiently oxidize center; electron-withdrawing -donating, depending oxidation state coordination geometry. These show enable key steps beyond imparting air-stability.Since documenting activity many observed unique this precatalyst. was found offer superior cross coupling form N,N-diaryl sulfonamides preparation biaryls from aryl halides benzene Ni-mediated, base-assisted homolytic aromatic substitution.

Язык: Английский

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Enantioselective Access to β-Amino Carbonyls via Ni-Catalyzed Formal Olefin Hydroamidation

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(21), С. 14745 - 14753

Опубликована: Май 14, 2024

We herein describe a Ni-catalyzed formal hydroamidation of readily available α,β-unsaturated carbonyl compounds to afford valuable chiral β-amino acid derivatives (up >99:1 e.r.) using dioxazolones as robust amino source. A wide range alkyl-substituted olefins conjugated esters, amides, thioesters, and ketones were successfully amidated at the β-position with excellent enantioselectivity for first time. Combined experimental computational mechanistic studies supported our working hypothesis that this unconventional β-amidation unsaturated substrates can be attributed polar-matched migratory olefin insertion an (amido)(Cl)Ni

Язык: Английский

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Regio- and Enantioselective Nickel-Catalyzed Ipso- and Remote Hydroamination Utilizing Organic Azides as Amino Sources for the Synthesis of Primary Amines

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Окт. 23, 2024

Primary amines serve as key synthetic precursors to most other

Язык: Английский

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Regioselective intermolecular carboamination of allylamines via nucleopalladation: empowering three-component synthesis of vicinal diamines

Chemical Science, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Intermolecular carboamination of allyl amines under Pd( ii )-catalysis is reported, expediting the synthesis vicinal diamines embedded in a functionally enriched linear carbon framework with high yields and exclusive Markovnikov selectivity.

Язык: Английский

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Three-component, stereoselective C–N bond forming alkene difunctionalization

Organic Chemistry Frontiers, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This review discusses emerging strategies in three-component, stereoselective C–N bond-forming alkene difunctionalization, emphasizing mechanistic innovations and their impact on synthetic organic chemistry.

Язык: Английский

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Nickel-Catalyzed Three-Component Carboamination/Cyclization of Alkynes To Access 2,3-Disubstituted Quinolines

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 23, 2025

Presented herein is a nickel-catalyzed chemo- and regioselective three-component tandem carboamination cyclization of terminal alkynes with organoboronic acids anthranils for facile modular access to 2,3-substituted quinolines. In this process, anthranil has dual roles: serving as an electrophilic aminating reagent redox buffer suppress the generation off-cycle Ni(0) complex. Moreover, anionic acetylacetonate (acac) ligand was found be vital ensure productive Ni(I)-Ni(III)-Ni(I) catalytic cycle.

Язык: Английский

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Rh(III)-Catalyzed Diastereo- and Enantioselective Regiodivergent (Hetero)Arylamidation of (Homo)Allylic Sulfides

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(14), С. 9768 - 9778

Опубликована: Март 28, 2024

A rhodium-catalyzed 3-component conjunctive diastereo- and regioselective arylamidation of (homo)allylic sulfides, organon boronic acids, dioxazolones is reported. These reactions deliver the 1,2-insertion 2,1-insertion products, respectively, for allylic sulfides homoallylic sulfides. The enantioselective terminal internal achieved, furnishing various 1,3-N,S compounds featuring one or two contiguous stereocenters in high yields with enantioselectivities. Mechanistic studies suggest a change turnover-limiting selectivity-determining steps induced by native easily removable sulfide group.

Язык: Английский

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Recent Advances in Nonprecious Metal Catalysis

Organic Process Research & Development, Год журнала: 2024, Номер unknown

Опубликована: Дек. 7, 2024

As the field of nonprecious metal catalysis continues to expand, we pursue a review series covering selected transformations in this area over short time interval highlight practical advancements. We seek raise awareness both current art and need continue development toward broader applications earth-abundant metals chemical pharmaceutical industries.

Язык: Английский

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