Installing the “magic methyl” – C–H methylation in synthesis

Chemical Society Reviews, Год журнала: 2021, Номер 50(9), С. 5517 - 5563

Опубликована: Янв. 1, 2021

Following notable cases of remarkable potency increases in methylated analogues lead compounds, this review documents the state-of-the-art C–H methylation technology.

Язык: Английский

---

Cobalt(III)-Catalyzed Regioselective C6 Olefination of 2-Pyridones Using Alkynes: Olefination/Directing Group Migration and Olefination

Organic Letters, Год журнала: 2021, Номер 23(12), С. 4624 - 4629

Опубликована: Июнь 9, 2021

Co(III)-catalyzed highly regio- and stereoselective direct C6 olefination of 2-pyridones with alkynes has been developed the assistance chelation. Upon variation reaction conditions, react well diaryl via a olefination/directing group migration pathway to give tetrasubstituted 6-vinyl-2-pyridones, but C6-H terminal works effectively afford only C6-olefinated 2-pyridones. A judicious choice solvent an additive is crucial for catalysis. The protocols feature 100% atom economy, excellent site selectivity, high stereoselectivity, ample substrate scope, good compatibility functional groups. Synthetic applications are demonstrated, experimental studies density theory calculations conducted gain mechanistic insight into two transformations.

Язык: Английский

---

Nickel-Catalyzed Decarbonylative Thioetherification of Carboxylic Acids with Thiols

The Journal of Organic Chemistry, Год журнала: 2022, Номер 87(13), С. 8672 - 8684

Опубликована: Июнь 18, 2022

A nickel-catalyzed decarbonylative thioetherification of carboxylic acids with thiols was developed. Under the reaction conditions, benzoic acids, cinnamic and benzyl coupled various including both aromatic aliphatic ones produce corresponding thioethers in up to 99% yields. Moreover, this applicable modification bioactive molecules such as 3-methylflavone-8-carboxylic acid, probenecid, flufenamic synthesis acaricide chlorbenside. These results well demonstrated potential synthetic value new organic synthesis.

Язык: Английский

---

Rhodium-Catalyzed C(sp²)–H Alkoxycarbonylation/Acylation of Indolines with Anhydrides as a Carbonyl Source

Organic Letters, Год журнала: 2022, Номер 24(5), С. 1141 - 1145

Опубликована: Янв. 31, 2022

We developed rhodium-catalyzed alkoxylcarbonylation/acylation of indolines using anhydrides as a safe and easy-to-handle carbonyl source. This catalytic process represents an additive- CO-free carbonylation, establishing simple straightforward protocol for synthesizing C7-carbonylated indolines. Notably, this reaction provides successful example C-H acylation that results in the formation α-branched ketones, which were difficult to prepare by previously reported analogous reactions.

Язык: Английский

---

Selective Pyridine-Directed C–H Activation Enabled Synthesis of Pyridine-pyridone α-Helix Mimics

Synlett, Год журнала: 2025, Номер unknown

Опубликована: Янв. 27, 2025

Abstract The exploration of pyridine-directed C–H activation in 2-benzyl-6-phenylpyridine revealed selective bromination at the ortho-phenyl position via Rh catalysis, rather than ortho-benzyl position. In contrast, corresponding alkylation was unsuccessful, suggesting a preference for Rh(III) pathway to minimize steric congestion from pyridine disubstitution. This mechanistic insight facilitated development room-temperature activation–bromination method, enabling synthesis pyridine-pyridone α-helix mimic.

Язык: Английский

---

Hybrid Pincer (PNN)Ni(II) Complex Catalyzed Selective C–H Alkylation of Pyridones Using Unactivated Alkyl Chlorides

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 2987 - 2999

Опубликована: Фев. 5, 2025

Язык: Английский

---

Catalytic Decarbonylative Functionalization of C–H Bonds with Carboxylic Acids

Synlett, Год журнала: 2025, Номер unknown

Опубликована: Март 31, 2025

Abstract Within the past decades, potential of transition-metal-catalyzed cross-coupling reactions using carboxylic acids as coupling partners has been subjected to extensive exploitation because natural abundance, ready availability, nontoxicity, stability, structural diversity, and low cost acids. Notably, recent years have witnessed intense research interest in combination decarbonylation with direct C–H bond functionalization presence transition-metal catalysts for formation various C–C bonds release CO. The approach presents a powerful alternative existing repertoire via formation. In this Account, we highlight our achievements development decarbonylative under catalysis. 1 Introduction 2 Arylation Aryl Carboxylic Acids 3 Alkenylation Alkenyl 4 Alkylation Alkyl 5 Conclusion Outlook

Язык: Английский

---

Visible-light-promoted selective O-alkylation of 2-pyridones with α-aryldiazoacetates

Organic & Biomolecular Chemistry, Год журнала: 2020, Номер 19(2), С. 394 - 398

Опубликована: Дек. 8, 2020

A visible-light-promoted O-H insertion reaction between 2-pyridones and α-aryldiazoacetates has been developed. Upon visible light irradiation, the proceeds smoothly under mild catalyst-free conditions. wide scope of are well tolerated, various O-alkylated obtained with perfect selectivity good functional group tolerance. photoinduced radical process is probably responsible for excellent selectivity.

Язык: Английский

---

Tunable C–H arylation and acylation of azoles with carboxylic acids by Pd/Cu cooperative catalysis

Organic Chemistry Frontiers, Год журнала: 2021, Номер 8(11), С. 2543 - 2550

Опубликована: Янв. 1, 2021

Direct C–H arylation and acylation of azoles with carboxylic acids are achieved selectively through Pd/Cu cooperative catalysis: biaryls generated dppp as ligand, while biaryl ketones obtained high selectivity using dpph or Ph₂PCy ligand.

Язык: Английский

---

Manganese(I)‐Catalyzed Site‐Selective C6‐Alkenylation of 2‐Pyridones Using Alkynes via C−H Activation

Advanced Synthesis & Catalysis, Год журнала: 2021, Номер 363(10), С. 2586 - 2593

Опубликована: Март 9, 2021

Abstract A Mn(I)‐catalyzed chelation‐assisted direct C6−H alkenylation of 2‐pyridones with both terminal and internal alkynes in a highly regio‐ stereo‐selective manner has been developed. The catalytic system consisting Mn(CO) 5 Br catalyst KOAc additive allows 1‐(2‐pyridyl)‐2‐pyridones to undergo various methyl tert ‐butyl ether (MTBE) furnish the C6‐alkenylated 2‐pyridone products high yields, occurs CH 2 Cl at increased loadings. Mechanistic studies suggest involvement five‐membered organomanganese as key intermediate cycle. magnified image

Язык: Английский

---