Recent Advances in Nonprecious Metal Catalysis DOI
David J. Bernhardson, Aran K. Hubbell, Robert A. Singer

et al.

Organic Process Research & Development, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 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.

Language: Английский

Benchtop Nickel Catalysis Invigorated by Electron-Deficient Diene Ligands DOI
Camille Rubel, Wen‐Ji He, Steven R. Wisniewski

et al.

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(3), P. 312 - 326

Published: Jan. 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.

Language: Английский

Citations

7
Enantioselective Access to β-Amino Carbonyls via Ni-Catalyzed Formal Olefin Hydroamidation DOI
Xiang Lyu, Hoimin Jung, Dongwook Kim

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(21), P. 14745 - 14753

Published: May 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

Language: Английский

Citations

6
Regio- and Enantioselective Nickel-Catalyzed Ipso- and Remote Hydroamination Utilizing Organic Azides as Amino Sources for the Synthesis of Primary Amines DOI

Shi‐Chao Wang,

Lin Liu,

Mei Duan

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 23, 2024

Primary amines serve as key synthetic precursors to most other

Language: Английский

Citations

6
Regioselective intermolecular carboamination of allylamines via nucleopalladation: empowering three-component synthesis of vicinal diamines DOI Creative Commons
Shib Nath Saha,

Nityananda Ballav,

Suman Ghosh

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

Citations

4
Nickel-Catalyzed Three-Component Carboamination/Cyclization of Alkynes To Access 2,3-Disubstituted Quinolines DOI
Yang Gao, Jiale Xing, Yanping Huo

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

Citations

0
Three-component, stereoselective C–N bond forming alkene difunctionalization DOI

J. NA,

J. Kim, Seong‐Joon Kim

et al.

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

Citations

0
Rh(III)-Catalyzed Diastereo- and Enantioselective Regiodivergent (Hetero)Arylamidation of (Homo)Allylic Sulfides DOI
Xiaoyan Jia,

Gui-Lin Hao,

Mengxia Feng

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(14), P. 9768 - 9778

Published: March 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.

Language: Английский

Citations

2
Recent Advances in Nonprecious Metal Catalysis DOI
David J. Bernhardson, Aran K. Hubbell, Robert A. Singer

et al.

Organic Process Research & Development, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 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.

Language: Английский

Citations

0