Ni(cod)(duroquinone)-Catalyzed C–N Cross-Coupling for the Synthesis of <i>N</i>,<i>N</i>-Diarylsulfonamides

You, Tingting; Li, Junqi

doi:10.1021/acs.orglett.2c02670

Cited by 15 publications

(9 citation statements)

References 37 publications

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“…Pyridines ( 49 and 50 ) and thiophene ( 51 ) were also tolerated under our conditions. It was worth noting that a secondary sulfonamide, such as N -methyl sulfonamide ( 52 ), could also afford the desired product in good yield.…”

Section: Resultsmentioning

confidence: 99%

Ni-Catalyzed Photochemial Sulfamidation of Aryl Chlorides with Soluble Organic Amine as Base

Song,

Dong

et al. 2024

Organometallics

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Transition-metal-catalyzed sulfonamidation is an attractive approach for the synthesis of N-(hetero)aryl sulfonamides, which are present in many bioactive pharmaceuticals. However, most catalyst systems require the use of strongly basic alkoxide salts as base, which leads to problems of functional group compatibility and a lack of selectivity for sulfonamides containing multiple NH 2 groups. Here, we reported the Ni-catalyzed photochemical C−N coupling of (hetero)aryl chlorides with sulfonamides using mild organic amines as base without the addition of external photocatalyst. This Ni-catalyzed C−N coupling features a broad substrate scope (84 examples), excellent functional group tolerance, and high sulfonamide group selectivity. The utility of this approach in synthetic chemistry is demonstrated by the late-stage functionalization or synthesis of pharmaceutical molecules.

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Section: Resultsmentioning

confidence: 99%

Ni-Catalyzed Photochemial Sulfamidation of Aryl Chlorides with Soluble Organic Amine as Base

Song,

Dong

et al. 2024

Organometallics

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“…In 2022, Li reported the synthesis of N,N-diarylsulfonamides through Ni-catalyzed C−N cross coupling of sulfonamides and aryl bromides (Scheme 6A). 54 With electronically unbiased aryl halides, Ni(COD) 2 provided less than 5% of the desired product, but the use of Ni(COD)(DQ) as precatalyst resulted in 90% yield. The authors posit that DQ enhances the rate of reductive elimination of electron-neutral and electron-rich aryl halides and creates an electron-deficient Ni-center that coordinates more favorably to the sulfonamide.…”

Section: Reports From Other Laboratories That Are Enabled By Ni(cod)(dq)mentioning

confidence: 99%

“…In 2022, Li reported the synthesis of N , N -diarylsulfonamides through Ni-catalyzed C–N cross coupling of sulfonamides and aryl bromides (Scheme A) . With electronically unbiased aryl halides, Ni(COD) 2 provided less than 5% of the desired product, but the use of Ni(COD)(DQ) as precatalyst resulted in 90% yield.…”

Section: Air-stable Nickel(0) Precatalysts As Privileged Scaffolds In...mentioning

confidence: 99%

Benchtop Nickel Catalysis Invigorated by Electron-Deficient Diene Ligands

Rubel,

He,

Wisniewski

et al. 2024

Acc. Chem. Res.

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Metrics & MoreArticle Recommendations CONSPECTUS: Due to the rarity of precious metals like palladium, nickel catalysis is becoming an increasingly important player in organic synthesis, especially for the formation of bonds with sp 3 -hybridized carbon centers. Traditionally, catalytic processes involving active Ni( 0) species have relied on Ni(COD) 2 or in situ reduction of Ni(II) salts. However, Ni(COD) 2 is an air-and temperature-sensitive material that requires use in an inertatmosphere glovebox, and in situ reduction protocols of Ni(II) salts using metallic or organometallic reductants add additional complications to reaction development. This Account chronicles the development of air-stable Ni(0) precursors as replacements for Ni(COD) 2 or in situ reduction. Based on Schrauzer's seminal discovery of Ni(COD)(DQ) as an air-stable zerovalent organonickel complex, our research laboratories at Scripps Research and Bristol Myers Squibb have developed a class of precatalysts based on the Ni(COD)(EDD) (EDD = electron-deficient diene) framework, relying on the steric and electronic properties of the supporting diene to render the metal center stable to air, moisture, and even silica gel but reactive to ligand substitution and redox changes. The stable Ni(0) complexes can be accessed through ligand exchange with Ni(COD) 2 , through reduction of Ni(acac) 2 using DIBAL-H, or electrochemically via cathodic reduction of Ni(acac) 2 to Ni(COD) 2 , followed by addition of an EDD ligand in one pot. As a toolkit, the complexes demonstrate reactivity that is equivalent or enhanced compared to Ni(COD) 2 , catalyzing C−C and C−N cross-couplings, Miyaura borylations, C−H activations, and other transformations. Since the initial report on Ni(COD)(DQ), its reactivity in C(sp 2 )−CN activation, metallophotoredox, and electric field-induced cross-coupling have also been demonstrated. By incorporating the precatalyst toolkit into reaction discovery campaigns, our laboratories have been able to perform C(sp 3 )− S(alkyl) couplings and metallonitrenoid carboamination, both of which represent challenging transformations that were inaccessible with traditional phosphine, nitrogen, or electron-deficient olefin ligands. Computational and experimental studies demonstrate how the quinone ligands are hemilabile, adopting η 1 (O)-bound geometries to relieve steric strain or stabilize transition states and intermediates; redox-active, able to transiently oxidize the metal center; and electron-withdrawing or -donating, depending on metal oxidation state and coordination geometry. These studies show how the ligands enable key steps in catalysis beyond imparting airstability. Since our report documenting the catalytic activity of Ni(COD)(DQ), many other laboratories have also observed unique reactivity with this precatalyst. Ni(COD)(DQ) was found to offer superior reactivity to Ni(COD) 2 in C−N cross coupling to form N,N-diaryl sulfonamides and in preparation of biaryls from aryl halides and benzene through a Ni-mediated, base-assisted homolytic a...

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“…The widespread availability of Ni(cod)(DQ) has facilitated its rapid adoption . As a notable example, Strotman and colleagues at Merck developed an aryl nitrile isotope exchange reaction that employs Ni(cod)(DQ) as the catalyst of choice .…”

Section: Earth-abundant Metals As Replacements For Palladiummentioning

confidence: 99%

Collaboration as a Key to Advance Capabilities for Earth-Abundant Metal Catalysis

Chirik

Engle

Simmons

et al. 2023

Org. Process Res. Dev.

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Earth-abundant metal (EAM) catalysis can have profound impact in the pharmaceutical industry in terms of sustainability and cost improvements from replacing precious metals like palladium as well as harnessing the differential reactivity of first-row metals that allows for novel transformations to enable more efficient routes to clinical candidates. The strategy for building these capabilities within the process group at Bristol Myers Squibb is described herein, with the general plan of building a reaction screening platform, demonstrating scalability, and increasing mechanistic understanding of the reaction and catalyst activation. The development of catalytic transformations utilizing nickel, cobalt, and iron is described while highlighting the importance of collaboration with internal and external groups to advance EAM catalysis and impact our portfolio. The challenges and benefits of working with first-row transition metals, including metrics for the implementation of EAM catalysis, such as cost, process mass intensity, and commercial availability of catalysts and ligands, are discussed.

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Ni(cod)(duroquinone)-Catalyzed C–N Cross-Coupling for the Synthesis of N,N-Diarylsulfonamides

Cited by 15 publications

References 37 publications

Ni-Catalyzed Photochemial Sulfamidation of Aryl Chlorides with Soluble Organic Amine as Base

Ni-Catalyzed Photochemial Sulfamidation of Aryl Chlorides with Soluble Organic Amine as Base

Benchtop Nickel Catalysis Invigorated by Electron-Deficient Diene Ligands

Collaboration as a Key to Advance Capabilities for Earth-Abundant Metal Catalysis

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