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

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(5), С. 1322 - 1345

Опубликована: Янв. 1, 2023

Functionalization of alkenes/alkynes is a highly effective route to achieve molecular complexity. This review summarizes recent progresses on the 1,2-difunctionalization/hydrofunctionalization unactivated with C−S bond formation.

Язык: Английский

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

Organic Process Research & Development, Год журнала: 2023, Номер 27(7), С. 1160 - 1184

Опубликована: Март 20, 2023

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

Язык: Английский

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Nickel‐Catalyzed Enantioselective Reductive Alkyl‐Carbamoylation of Internal Alkenes

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(36)

Опубликована: Июль 12, 2022

Herein, we leverage the Ni-catalyzed enantioselective reductive dicarbofunctionalization of internal alkenes with alkyl iodides to enable synthesis chiral pyrrolidinones bearing vicinal stereogenic centers. The application newly developed

Язык: Английский

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

Advanced Science, Год журнала: 2024, Номер 11(29)

Опубликована: Июнь 9, 2024

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

Язык: Английский

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Directed copper-catalyzed C–H functionalization of unactivated olefins with azodicarbonamide compounds

RSC Advances, Год журнала: 2024, Номер 14(38), С. 27475 - 27480

Опубликована: Янв. 1, 2024

The copper-catalyzed strategy employing the 8-aminoquinoline directing group has proven to be a highly advantageous approach for functionalizing C-H bonds. In this study, we present successful application of accomplish Heck-type coupling reactions and construct β-lactam skeletons, simultaneously introducing unique cyano functional group. resulting products demonstrate good stereo- region-selectivity. Initial mechanistic investigations indicate that reaction proceeds

Язык: Английский

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Iron-Catalyzed Markovnikov-Selective Radical Hydrochalcogenation of Unactivated Alkenes

ACS Catalysis, Год журнала: 2024, Номер 15(1), С. 14 - 22

Опубликована: Дек. 12, 2024

A Markovnikov-selective radical hydrochalcogenation reaction of unactivated alkenes via iron-catalyzed hydrogen atom transfer was reported. Using N-(arylsulfenyl)arenesulfonamide, PhSO2SCD3, S-alkyl thiosulfonate, dithiosulfonate and Ebselen derivatives as versatile radicalophiles, a wide range unsymmetrical alkyl-aryl, dialkyl SCD3 (D > 99%) containing sulfides, disulfides, well organoselenides have been collectively synthesized under mild conditions. As powerful alternative to the classical thiol–ene reaction, this protocol features exclusive Markovnikov selectivity, good functional group tolerance broad substrate scope. number probe experiments suggest proceeds through pathway. The synthetic utility transformation also demonstrated late-stage modifications diverse natural products bioactive molecules.

Язык: Английский

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Directed Nickel-Catalyzed Selective Arylhydroxylation of Unactivated Alkenes under Air

Organic Letters, Год журнала: 2023, Номер 25(13), С. 2172 - 2177

Опубликована: Март 22, 2023

An expeditious and novel nickel-catalyzed selective arylhydroxylation of unactivated alkenes with arylboronic acids was developed. This protocol is compatible β,γ- γ,δ-alkene amides, including traditionally challenging internal alkenes, to provide important β-arylethylalcohol scaffolds. The free hydroxyl group in the final product could be smoothly further transformed into other functional groups. Control experiments indicated that oxygen atom derived from air.

Язык: Английский

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Nickel‐Catalyzed Enantioselective Reductive Alkyl‐Carbamoylation of Internal Alkenes

Angewandte Chemie, Год журнала: 2022, Номер 134(36)

Опубликована: Июль 12, 2022

Abstract Herein, we leverage the Ni‐catalyzed enantioselective reductive dicarbofunctionalization of internal alkenes with alkyl iodides to enable synthesis chiral pyrrolidinones bearing vicinal stereogenic centers. The application newly developed 1‐Nap Quinim is critical for formation two contiguous stereocenters in high yield, enantioselectivity, and diastereoselectivity. This catalytic system also improves both yield enantioselectivity α,α‐dialkylated γ‐lactams. Computational studies reveal that enantiodetermining step proceeds a carbamoyl‐Ni I intermediate reduced by Mn reductant prior intramolecular migratory insertion. presence t ‐butyl group ligand leads an unfavorable distortion substrate TS minor enantiomer. Calculations support improvement compared p ‐tol Quinim.

Язык: Английский

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1,2-Alkylsulfenylation and -Selenolation of Alkenes with Organozinc Nucleophiles

Synfacts, Год журнала: 2022, Номер 18(07), С. 0750 - 0750

Опубликована: Июнь 15, 2022

Key words nickel catalysis - alkene functionalization carbosulfenylation

Язык: Английский

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