α-Carbonyl sulfoxonium ylides in transition metal-catalyzed C–H activation: a safe carbene precursor and a weak directing group

Organic & Biomolecular Chemistry, Год журнала: 2022, Номер 21(5), С. 879 - 909

Опубликована: Дек. 6, 2022

Transition metal-catalyzed cross-coupling of sp2 C-H bonds with diazo compounds via carbene migratory insertion represents an efficient strategy for the construction C-C and C-heteroatom in organic synthesis. Despite popularity as coupling partners activation, they pose serious safety stability issues due to potential exothermic reactions linked release N2 gas. However, compared compounds, sulfoxonium ylides are generally crystalline solids, more stable, widely used industrial scales, easier/safer prepare. Therefore, recent years have witnessed upsurge employing α-carbonyl alternative surrogate transition activation. Unlike contain inherent serve a partner well weak directing group. This review will summarize progress made both categories reactions.

Язык: Английский

---

Substituted Isocoumarins: An Assemble of Synthetic Strategies Towards 3‐Substituted and 3,4‐Disubstituted Isocoumarins

Chemistry - An Asian Journal, Год журнала: 2023, Номер 18(5)

Опубликована: Янв. 17, 2023

The versatility of isocoumarin frameworks offers the privilege to access many pharmacological targets. This unique heterocycle core present in natural products and complex organic molecules contribute medicinal chemistry as anti-cancer, anti-inflammatory immunomodulatory agents. attractive properties exhibited by its analogues urged scientists explore their synthetic analogues. In regard myriads methodologies, we have compiled a review update covering all articles that been published towards synthesis 3-substituted 3,4-disubstituted isocoumarins. Additionally, also highlighted systematic survey catalytic methods for along with scope diverse functionalizations plausible mechanistic aspects.

Язык: Английский

---

Catalytic Asymmetric C–H Activation/Cyclization of Sulfoximines with Sulfoxonium Ylides by a Chiral η⁶-Benzene Ruthenium(II) Catalyst

ACS Catalysis, Год журнала: 2024, Номер unknown, С. 17398 - 17404

Опубликована: Ноя. 12, 2024

Chiral η6-benzene ruthenium(II) (BenRuII)-catalyzed asymmetric C–H activations are challenging and rarely seen in the literature. Herein, activation/cyclization of sulfoximines with sulfoxonium ylides catalyzed by chiral BenRuII catalyst derived from (S)-H8–BINOL is described. It provides efficient access to various sulfur-chiral 1,2-benzothiazine 1-oxides high yields enantioselectivities (up 99% yield 98% ee). Kinetic resolution racemic was also feasible. The reaction mechanism studied tool H/D exchange kinetic isotope effect. metallacycle revealing origin induction prepared, characterized, proved effective for model reaction. This work demonstrates great potential catalysts activation.

Язык: Английский

---

Hydroxyl-Directed Ruthenium-Catalyzed peri-Selective C–H Acylmethylation and Annulation of Naphthols with Sulfoxonium Ylides

Organic Letters, Год журнала: 2021, Номер 23(16), С. 6200 - 6205

Опубликована: Авг. 2, 2021

Herein, we report a highly efficient ruthenium-catalyzed peri-selective C(sp2)–H acylmethylation of 1-naphthols with α-carbonyl sulfoxonium ylides by utilizing hydroxyl as weakly coordinating directing group. This new method imparts good reactivity, excellent chemo- and regioselectivity, broad functional group tolerance involves mild reaction conditions. The C–H acylmethylated products can be readily cyclized into fluorescent annulated pyrans one-pot process.

Язык: Английский

---

Synthesis of Tetrahydro-2H-thiopyran 1,1-Dioxides via [1+1+1+1+1+1] Annulation: An Unconventional Usage of a Tethered C–S Synthon

Organic Letters, Год журнала: 2022, Номер 24(41), С. 7659 - 7664

Опубликована: Окт. 10, 2022

An unprecedented [1+1+1+1+1+1] annulation process has been developed for the construction of tetrahydro-2H-thiopyran 1,1-dioxides. Notably, rongalite acted as a tethered C-S synthon in this reaction and can be chemoselectively used triple C1 units source sulfone. Mechanistic investigation indicated that two different carbon-increasing models are involved which serves units.

Язык: Английский

---

Regioselective and Chemodivergent Synthesis of Azulenolactones and Azulenolactams from Rhodium(III)‐Catalyzed Reactions of Azulenecarboxamides with Sulfoxonium Ylides

Advanced Synthesis & Catalysis, Год журнала: 2020, Номер 363(2), С. 512 - 524

Опубликована: Ноя. 4, 2020

Abstract A regioselective and chemodivergent synthetic approach for azulenolactones azulenolactams as a new scaffold was demonstrated through Rh(III)‐catalyzed reaction of N ‐methoxyazulene‐1‐carboxamides with sulfoxonium ylides. Sulfoxonium ylides that act precursor secondary carbene described, leading to the selective formation bearing two substituents on newly introduced double bond. This method functionalization less reactive 2‐position azulene overcome natural reactivity. magnified image

Язык: Английский

---

Recent Advances on Synthetic Methodology Merging C–H Functionalization and C–C Cleavage

Molecules, Год журнала: 2020, Номер 25(24), С. 5900 - 5900

Опубликована: Дек. 13, 2020

The functionalization of C–H bonds has become a major thread research in organic synthesis that can be assessed from different angles, for instance depending on the type catalyst employed or overall transformation is carried out. This review compiles recent progress synthetic methodology merges along with cleavage C–C bonds, either intra- intermolecular fashion. manuscript organized two main sections according to substrate which bond takes place, basically attending scission strained unstrained bonds. Furthermore, related works have been grouped basis mechanistic aspects transformations are out, i.e.,: (a) classic transition metal catalysis where organometallic intermediates involved; (b) processes occurring via radical generated through use initiators photochemically; and (c) reactions catalyzed mediated by suitable Lewis Brønsted acid bases, molecular rearrangements take place. Thus, throughout wide range approaches show combination single operations serve as platform achieve complex skeletons straightforward manner, among them interesting carbo- heterocyclic scaffolds.

Язык: Английский

---

Easy synthesis of imidazo[1,5-a]indol-3-ones through Rh(iii)-catalyzed C–H allenylation/annulation

Chemical Communications, Год журнала: 2021, Номер 57(90), С. 12012 - 12015

Опубликована: Янв. 1, 2021

A highly efficient and regioselective synthesis of imidazo[1,5-a]indol-3-ones has been developed via a sequential C-H allenylation/annulation starting from easily available N-methoxycarbamoyl indoles propargyl alcohols, in which the alcohols served as C1 synthon. This strategy displays excellent regioselectivity, high atom economy tolerates broad substrate scope.

Язык: Английский

---

Recent advances in synthesis of isocoumarins: An overview

Tetrahedron, Год журнала: 2023, Номер 150, С. 133740 - 133740

Опубликована: Ноя. 12, 2023

Язык: Английский

---

Quinazolinone-to-Isoquinoline Metamorphosis by Ruthenium-Catalyzed [4+2] Annulation with Sulfoxonium Ylides

Organic Letters, Год журнала: 2024, Номер 26(50), С. 10951 - 10957

Опубликована: Дек. 10, 2024

Molecular editing of quinazolinones to isoquinolines by a novel ruthenium-catalyzed [4+2] annulation with sulfoxonium ylides has been developed. The method permits the precise and rapid assembly multisubstituted aminoisoquinolines, class heterocycles that play privileged role in organic synthesis pharmaceutical development. This new catalytic process exhibits programmability, including directed C–H acetylation, nucleophilic cyclization, alcoholysis. Remarkably, various 2-arylquinazolinones could be employed excellent yields broad functional group tolerance. heterocycle-to-heterocycle protocol is compatible green chemistry using an EtOH solvent releasing H2O dimethyl sulfoxide as byproducts.

Язык: Английский

---