Ni-catalyzed C–S bond construction and cleavage

Chemical Society Reviews, Год журнала: 2022, Номер 51(19), С. 8351 - 8377

Опубликована: Янв. 1, 2022

This review focuses on nickel-catalyzed construction and transformation of various sulfide-containing compounds, such as sulfides, disulfides, hypervalent sulfur-containing compounds.

Язык: Английский

---

Sulfonium Salts as Acceptors in Electron Donor‐Acceptor Complexes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(29)

Опубликована: Март 24, 2023

Abstract The photoactivation of electron donor‐acceptor complexes has emerged as a sustainable, selective and versatile strategy for the generation radical species. Electron (EDA) complexation, however, imposes electronic constraints on donor acceptor components this can limit range radicals that be generated using approach. New EDA complexation strategies exploiting sulfonium salts allow to from native functionality. For example, aryl salts, formed by activation arenes, serve in due their electron‐deficient nature. This “sulfonium tag” approach relaxes parent substrate dramatically expands complexation. In review, these new applications will introduced areas chemical space rendered accessible through innovation highlighted.

Язык: Английский

---

Aryl sulfonium salt electron donor-acceptor complexes for halogen atom transfer: Isocyanides as tunable coupling partners

Chem, Год журнала: 2024, Номер 10(4), С. 1240 - 1251

Опубликована: Фев. 13, 2024

The photoactivation of sulfonium salt EDA (electron donor-acceptor) complexes provides a mild platform for aryl-radical-mediated halogen atom transfer activation wide range functionalized alkyl iodides, including tertiary iodides. Using an aryl with carbonate as inexpensive donor complex formation, the general reaction has been applied in divergent, metal-free photochemical approach to nitriles and amides. This divergency was made possible by tuning isocyanide radical traps. For example, identification readily accessible, bench-stable, crystalline amide containing grants access nitrile products complete selectivity.

Язык: Английский

---

N‐(Sulfonio)Sulfilimine Reagents: Non‐Oxidizing Sources of Electrophilic Nitrogen Atom for Skeletal Editing

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(25)

Опубликована: Апрель 16, 2024

The one-pot synthesis of λ

Язык: Английский

---

Revisiting Aromatic Claisen Rearrangement Using Unstable Aryl Sulfonium/Iodonium Species: The Strategy of Breaking Up the Whole into Parts

Accounts of Chemical Research, Год журнала: 2022, Номер 55(15), С. 2103 - 2122

Опубликована: Июль 21, 2022

ConspectusSince Ludwig Claisen's discovery of the sigmatropic rearrangement allyl aryl ethers in 1912, aromatic Claisen has continuously attracted attention both experimental and theoretical chemists. Over more than a century growth, this protocol proven to be practical powerful synthetic tool many aspects. However, reaction scope long been limited their S or N analogs until serendipitous iodonium-Claisen by Oh et al. 1988 development sulfonium-Claisen Kita 2004. Unlike traditional rearrangements, these hypervalent-bonding-based Claisen-type rearrangements can performed simply mixing electrophilically activated sulfoxides/iodanes with certain nucleophiles directly deliver products. In addition simple operation, remarkable features, such as readily available substrates, valuable products intriguing patterns, have led dramatic resurgence chemistry.In Account, we summarize our recent works on developing new modes using sulfonium/iodonium reagents. Interestingly, program started an accidental that sulfoxides could coupled alkyl nitriles presence Tf2O base. Mechanistic studies reveal proceeds three major steps, including Tf2O-triggered assembly coupling partners, base-promoted deprotonation situ-generated sulfonium-imine species leading key precursor called sulfonium-ketenimine species, subsequent facile rapid [3,3]-rearrangement. On basis mechanistic underpinning, divided one-step operation into two steps "assembly/deprotonation" for constructing unstable precursors. Most notably, switch from commonly used mechanism-based multiple-step manipulation, which termed "breaking up whole parts", not only enables independent control each step reaction, thus significantly expanding accessible scope, but also raises opportunities patterns. For example, applied [5,5]-rearrangement asymmetric iodanes, enabling unprecedented regio- stereocontrol process. Furthermore, parts" thinking triggered us merge Morita-Baylis-Hillman (MBH) process accomplish Z-selective MBH-type [3,3]-rearrangement α,β-unsaturated E-selective 2-oxazolines, expands partners include carbonyls. addition, impressive rapidity found initial recognized congestion-acceleration effect, was further utilized forge ortho-cyanoalkylative first dearomatization iodanes. We anticipate protocols ideas behind methods will complementary rearrangement.

Язык: Английский

---

Access to Benzyl Oxindoles via Electron Donor‐Acceptor Complex Photoactivation Using Thianthrenium Salts and Potassium Carbonate

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(11), С. 2587 - 2595

Опубликована: Апрель 19, 2024

Abstract A photochemical synthesis of biologically relevant benzyl oxindoles is presented via electron‐donor acceptor (EDA) complex strategy. This exogenous photocatalyst‐free method describes the formation a new electron donor‐acceptor based on potassium carbonate and thianthrenium salts for C( sp 2 )−C( 3 ) bond formation. transition‐metal free reaction allows rapid increase in molecular complexity chemical space, tolerating different functional groups as well sophisticated biomolecules. The scalability sustainability this highlighted by an important waste recovery protocol. Mechanistic investigations support EDA that induces radical chain, applicability showcased straightforward derivatization reactions.

Язык: Английский

---

Stereoretentive Conversion to C-Glycosides from S-Glycosides via Ligand-Coupling on Sulfur(IV)

Organic Letters, Год журнала: 2025, Номер 27(4), С. 954 - 960

Опубликована: Янв. 21, 2025

A novel strategy is reported for the stereoselective synthesis of C(sp2)-C(sp3) C-glycosides, which converts heteroaryl S-glycosides into C-glycosides with retention configuration through a sequential process involving oxidation and Grignard reagent attack. The new method involves generation S(IV) intermediate, followed by ligand coupling glycosyl groups to yield C-glycosides. diverse were achieved good efficiency.

Язык: Английский

---

Metal‐Free Arylation of Benzothiophenes at C4 by Activation as their Benzothiophene S‐Oxides

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(29)

Опубликована: Март 31, 2023

Abstract Benzothiophenes, activated by oxidation to the corresponding S ‐oxides, undergo C−H/C−H‐type coupling with phenols give C4 arylation products. While an electron‐withdrawing group at C3 of benzothiophene is important, process operates without a directing and metal catalyst, thus rendering it compatible sensitive functionalities—e.g. halides formyl groups. Quantum chemical calculations suggest formal stepwise mechanism involving heterolytic cleavage aryloxysulfur species π‐complex phenoxonium cation. Subsequent addition cation position favored over C3; Fukui functions predict that major regioisomer formed more electron‐rich between C4. Varied selective manipulation products showcase synthetic utility metal‐free process.

Язык: Английский

---

Cathodically Coupled Electrolysis to Access Biheteroaryls

Organic Letters, Год журнала: 2024, Номер 26(3), С. 607 - 612

Опубликована: Янв. 11, 2024

An electrochemical approach to biheteroaryls through the coupling of diverse N-heteroarenes with heteroaryl phosphonium salts is reported. The reaction features pH and redox-neutral conditions excellent regioselectivity, as well exogenous air or moisture tolerance. Additionally, a one-pot, two-step protocol can be established realize formal C–H/C–H heteroarenes, thereby greatly expanding substrate availability. utility this method demonstrated late-stage functionalization, total synthesis nitraridine, antifungal activity studies.

Язык: Английский

---

Synthetic application of chalcogenonium salts: beyond sulfonium

Organic & Biomolecular Chemistry, Год журнала: 2022, Номер 21(2), С. 223 - 236

Опубликована: Дек. 6, 2022

The application of chalcogenonium salts in organic synthesis has grown enormously the past decades since discovery methyltransferase enzyme cofactor S-adenosyl-L-methionine (SAM), featuring a sulfonium center as reactive functional group. Chalcogenonium can be employed alkylating agents, sources ylides and carbon-centered radicals, partners for metal-catalyzed cross-coupling reactions organocatalysts. Herein, we will focus discussion on heavier (selenonium telluronium), presenting their utility synthetic transformations and, whenever possible, drawing comparisons terms reactivity selectivity with respective analogues.

Язык: Английский

---