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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Recent advances in thiolation via sulfur electrophiles

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(23), С. 6684 - 6707

Опубликована: Янв. 1, 2022

This review systematically summarizes the recent developments for constructing sulfur compounds from electrophiles, and mechanism mainly involved thirranium ions, ylides, C–S cross coupling electrophilic substitution.

Язык: Английский

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Ni- and Pd-Catalyzed Enantioselective 1,2-Dicarbofunctionalization of Alkenes

Synthesis, Год журнала: 2023, Номер 56(01), С. 1 - 15

Опубликована: Июнь 12, 2023

Abstract Catalytic enantioselective 1,2-dicarbofunctionalization (1,2-DCF) of alkenes is a powerful transformation growing importance in organic synthesis for constructing chiral building blocks, bioactive molecules, and agrochemicals. Both two- three-component context, this family reactions generates densely functionalized, structurally complex products single step. Across several distinct mechanistic pathways at play these transformations with nickel or palladium catalysts, stereocontrol can be obtained through tailored ligands. In Review we discuss the various strategies, mechanisms, catalysts that have been applied to achieve enantioinduction alkene 1,2-DCF. 1 Introduction 2 Two-Component Enantioselective 1,2-DCF via Migratory Insertion 3 Radical Capture 4 Three-Component 5 6 Miscellaneous Mechanisms 7 Conclusion

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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Modular and Practical 1,2‐Aryl(Alkenyl) Heteroatom Functionalization of Alkenes through Iron/Photoredox Dual Catalysis**

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(44)

Опубликована: Сен. 13, 2023

Abstract Efficient methods for synthesizing 1,2‐aryl(alkenyl) heteroatomic cores, encompassing heteroatoms such as nitrogen, oxygen, sulfur, and halogens, are of significant importance in medicinal chemistry pharmaceutical research. In this study, we present a mild, versatile practical photoredox/iron dual catalytic system that enables access to highly privileged pharmacophores with exceptional efficiency site selectivity. Our approach exhibits an extensive scope, allowing the direct utilization wide range commodity or commercially available (hetero)arenes well activated unactivated alkenes diverse functional groups, drug scaffolds, natural product motifs substrates. By merging iron catalysis photoredox cycle, vast array alkene functionalization products incorporate neighboring azido, amino, halo, thiocyano nitrooxy group were secured. The scalability ability rapid synthesize numerous bioactive small molecules from readily starting materials highlight utility protocol.

Язык: Английский

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Nitrative Difunctionalization of Alkenes via Cobalt-Mediated Radical Ligand Transfer and Radical-Polar Crossover Photoredox Catalysis

ACS Catalysis, Год журнала: 2023, Номер 13(24), С. 16136 - 16147

Опубликована: Дек. 1, 2023

Herein, we report the rational design of a modular dual photoredox and cobalt catalysis paradigm for difunctionalization unsaturated hydrocarbons, unlocking synthesis valuable but challenging 1,2-halonitroalkane substrate class. The protocol relies on use redox-active organic nitrating reagent N-nitrosuccinimide as source nitryl radicals cobalt-mediated radical ligand transfer (RLT) methodology to form carbon–halogen bond. This synergistic cooperation between photocatalyst high-valence metal center occurs under mild reaction conditions is capable delivering 1,2-chloronitro- 1,2-bromonitroalkanes in single chemical operation while exhibiting high functional-group tolerance exclusive regioselectivity variety olefins. Mechanistic studies based both experimental spectroscopic analysis provided insights into nature this catalytic halo-nitration process including evidence halogen catalyst. Furthermore, employing net-neutral radical/polar crossover (RPC) approach cobalt-free allowed us accommodate external protic nucleophiles, thiols, alcohols, acids, and, notably, substituted amines. Highly functionalized olefin scaffolds also successfully underwent nitrative difunctionalization, demonstrating viability these protocols late-stage functionalization bioactive molecules.

Язык: Английский

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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 Ni‐Catalyzed Three‐Component Dicarbofunctionalization of Alkenes

ChemCatChem, Год журнала: 2023, Номер 15(18)

Опубликована: Авг. 3, 2023

Abstract Asymmetric multicomponent reactions are considered as efficient protocols for constructing complex chiral molecules because of their step‐ and atom‐economy. Nickel‐catalyzed asymmetric three‐component dicarbofunctionalization alkenes has been well developed in recent years, which is used the area total synthesis natural products late‐stage modification drugs rapid incorporation sp 3 ‐enriched carbon centers. In this concept, significant breakthroughs field summarized, together with related mechanisms. Moreover, remaining challenges potential opportunities also highlighted.

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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Catalytic Enantioselective Intermolecular Three-Component Sulfenylative Difunctionalizations of 1,3-Dienes

ACS Catalysis, Год журнала: 2023, Номер 13(4), С. 2715 - 2722

Опубликована: Фев. 7, 2023

This work demonstrates regio- and enantioselective intermolecular three-component oxysulfenylations of 1,3-dienes with alcohols, phenols, acids, water as O-nucleophiles. These reactions were enabled by the cooperative catalysis chiral sulfide phosphoric acid. Various useful sulfur-containing allylic ethers, esters, alcohols readily obtained in moderate to excellent yields high enantioselectivities regioselectivities. protocol provides chemo-, regio-, together a broad scope good functional group compatibility.

Язык: Английский

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