Directed, nickel-catalyzed 1,2-alkylsulfenylation of alkenyl carbonyl compounds

Li, Ziqi; He, Wen-Ji; Ni, Hui‐Qi; Engle, Keary M.

doi:10.1039/d2sc01563c

Cited by 11 publications

(2 citation statements)

References 70 publications

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“…This endeavor has been very productive, leading to a series of publications and pushing the state of the art in the directing-auxiliary-free diarylation of alkenyl amides, carboxylates and ketones, for example. Through our work in this field, we learned the importance of an electron-deficient olefin, showcasing the ability of Ni(cod)(DMFU) to serve as a catalyst in challenging diarylations . While the initial goal of the precatalyst project was to develop Ni(0) complexes that were more stable but otherwise functionally equivalent to Ni(cod) 2 , we and others have found that quinone-ligated nickel centers possess unique reactivity in important reactions, such as the aforementioned difunctionalization of alkenes and nickel-catalyzed C–N couplings, which is a phenomenon we are now exploring in depth through our collaboration.…”

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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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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“…C–S bond formation via the reductive elimination regenerated the active Ni( i ) catalyst ( 244 ). Soon after that, the Engle group 72 further expanded the scope of the nucleophile to C(sp 3 ) partners and developed the 1,2-alkylsulfenylation of unactivated alkenes with alkylzinc reagents and the sulfonamide sulfenyl electrophiles. To surrogate the above mentioned undesired process and the β-hydride elimination of alkyl nucleophile, a stronger bidentate directing auxiliary (8-aminoquinoline, AQ) was employed.…”

Section: Transition-metal Catalyzed Carbosulfenylationmentioning

confidence: 99%

Recent developments on 1,2-difunctionalization and hydrofunctionalization of unactivated alkenes and alkynes involving C–S bond formation

2023

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Stabilized Carbon‐Centered Radical‐Mediated Carbosulfenylation of Styrenes: Modular Synthesis of Sulfur‐Containing Glycine and Peptide Derivatives

Yang,

Liu,

Xie

2024

Advanced Science

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Sulfur‐containing amino acids and peptides play critical roles in organisms. Thiol‐ene reactions between the thiol residues of L‐cysteine and the alkenyl fragments in the designed coupling partners serve as primary tools for constructing C─S bonds in the synthesis of unnatural sulfur‐containing amino acid derivatives. These reactions are favored due to the preference for hydrogen transfer from thiol to β‐sulfanyl carbon radical intermediates. In this paper, the study proposes utilizing carbon‐centered radicals stabilized by the capto‐dative effect, generated under photocatalytic conditions from N–aryl glycine derivatives. The aim is to compete with the thiol hydrogen, enabling radical C─C bond formation with β‐sulfanyl carbon radicals. This protocol is robust in the presence of air and water, offers significant potential as a modular and efficient platform for synthesizing sulfur‐containing amino acids and modifying peptides, particularly with abundant disulfides and styrenes.

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Directed, nickel-catalyzed 1,2-alkylsulfenylation of alkenyl carbonyl compounds

Abstract: We report a regioselective, nickel-catalyzed syn-1,2-carbosulfenylation of non-conjugated alkenyl carbonyl compounds with alkyl/arylzinc nucleophiles and tailored N–S electrophiles. This method allows the simultaneous installation of a variety of C(sp3) and...

Cited by 11 publications

References 70 publications

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

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

Recent developments on 1,2-difunctionalization and hydrofunctionalization of unactivated alkenes and alkynes involving C–S bond formation

Stabilized Carbon‐Centered Radical‐Mediated Carbosulfenylation of Styrenes: Modular Synthesis of Sulfur‐Containing Glycine and Peptide Derivatives

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