Visible-Light-Induced Siloxycarbene Addition to N═N of Azodicarboxylates: Synthesis of Acyl Hydrazides from Acylsilanes

Organic Letters, Год журнала: 2024, Номер 26(10), С. 2039 - 2044

Опубликована: Март 4, 2024

We report the synthesis of acyl hydrazides from acylsilanes in presence visible light without aid additives or transition metals. Acylsilanes underwent [1,2]-Brook rearrangement to generate nucleophilic siloxycarbenes which on further addition N═N azodicarboxylates produced hydrazides. Control experiments indicate that reaction proceeds through singlet carbene intermediate. Transformation hydrazide functionality other functional groups was demonstrated, including drug candidate Moclobemide.

Язык: Английский

---

Light-induced arylation (alkylation) of N-sulfonylhydrazones with boronic acids

Chemical Communications, Год журнала: 2024, Номер 60(20), С. 2796 - 2799

Опубликована: Янв. 1, 2024

We report light-induced arylation (alkylation) for the synthesis of diarylmethanes, bis(diarylmethyl)benzenes, arylalkylmethanes, and triarylmethanes from readily accessible N -sulfonylhydrazones aryl/alkylboronic acids with aid Cs 2 CO 3 .

Язык: Английский

---

Mechanistic Insights Into the B(C₆F₅)₃‐catalyzed Wolff Rearrangement/[2 + 2] and [4 + 2] Cascade Cyclization of α‐Diazoketones With Imines

Chemistry - An Asian Journal, Год журнала: 2025, Номер unknown

Опубликована: Апрель 21, 2025

Presented herein is a DFT investigation of the B(C6F5)3-catalyzed system involving Wolff rearrangement/[2 + 2] and [4 cascade cyclization α-diazoketones with imines. The study provides detailed elucidation ketene formation through B(C6F5)3-promoted rearrangement α-diazoketones, alongside substrate-dependent chemoselectivity observed in reveals three-step process, B-O adduct formation, carbene species generation via N2 extrusion facile 1,2-migration. Computational studies successfully replicate experimentally resulting intermediate different N-protected Notably, N-tert-butoxycarbonyl imines exhibit preferential stepwise [2 cyclization, while N-tert-butylcarbonyl favor concerted cycloaddition. divergence these reactions rationalized distortion/interaction analysis critical transition states.

Язык: Английский

---

gem-Difluoro-Masked o-Quinone Methides Generated by Photocatalytic Radical (3+3) Annulation and Their (4+1) Cycloaddition with Sulfur Ylides

Organic Letters, Год журнала: 2023, Номер 25(48), С. 8700 - 8705

Опубликована: Ноя. 23, 2023

A visible light-promoted radical (3+3) annulation of vinyldiazo compounds and bromodifluoromethyl alkynyl ketones for the construction gem-difluoro-masked o-quinone methides (o-QMs) is described. The reactivity this new type o-QM precursor demonstrated by its (4+1) cycloaddition with sulfur ylides, affording monofluorinated aromatic benzofurans elimination HBr without external oxidants.

Язык: Английский

---

Palladium-catalyzed [4+4] cycloaddition of 2-pyrones with 2-alkylidenetrimethylene carbonates: access to bridged eight-membered oxygen heterocycles

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(10), С. 2864 - 2869

Опубликована: Янв. 1, 2024

A novel palladium-catalyzed [4 + 4] cycloaddition of 2-pyrones with 2-alkylidenetrimethylene carbonates has been developed for the synthesis bridged eight-membered oxygen heterocycles in good yields and excellent stereoselectivities.

Язык: Английский

---

Transition metal-catalyzed reactivity of carbenes with boronic acid derivatives for arylation (alkylation) and beyond

Organic & Biomolecular Chemistry, Год журнала: 2023, Номер 21(35), С. 7062 - 7078

Опубликована: Янв. 1, 2023

This review summarizes the transition metal-catalyzed reactivity of carbenes with different boronic acids and esters to form carbon–carbon bonds, carbon–boron beyond.

Язык: Английский

---

Synthesis of Hypervalent Iodine Diazo Compounds and Their Application in Organic Synthesis

Chemistry - A European Journal, Год журнала: 2023, Номер 30(5)

Опубликована: Окт. 17, 2023

Diazomethyl-substituted iodine(III) compounds with electron-withdrawing groups (EWG) connected to diazo methyl center were a type of donor-acceptor potential reaction abilities similar ordinary compounds. Although several diazomethyl-substituted synthesized and used in the nucleophilic substitution reactions as early 1994, synthesis application new have only been reported certain extent recent years. In presence rhodium catalyst, photocatalyst, or nucleophiles, can be converted into rhodium-carbenes, diazomethyl radicals, ester radicals intermediates, which key intermediates for formation chemical bonds. The aim this review is give an overview organic synthesis.

Язык: Английский

---

Heterogeneous Catalysis in the Synthesis of Nitrogen‐Containing Heterocyclics

ChemistrySelect, Год журнала: 2024, Номер 9(41)

Опубликована: Окт. 28, 2024

Abstract The synthesis of nitrogen‐containing heterocyclic compounds using heterogeneous catalysis is a topic significant interest in organic and chemical research. Heterogeneous offers several advantages over homogeneous catalysis, including easier separation recovery the catalyst, reduced waste generation, potentially higher stability reusability. In this review, pivotal role synthesizing explored. Various types heterocycles specific applications these drug discovery material development are discussed detail. This review discusses various examples catalysts employed heterocycles, metal oxides, supported metals, nanoparticles, zeolites, other porous materials. Emphasis placed on mechanistic insights reaction pathways facilitated by different catalysts. Additionally, recent advancements innovations field discussed, novel catalyst designs, green chemistry approaches, emerging trends catalytic aim to provide comprehensive overview impact potential important area synthesis.

Язык: Английский

---

Light-Induced Reactivity of Nucleophilic Siloxycarbene with Heterocumulenes: Synthesis of α-Ketoamides, Hydantoins, Oxoacetamidines, and Amides

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 25, 2024

We report the reactivity of in situ-generated nucleophilic siloxycarbenes from acylsilanes via 1,2-Brook rearrangement presence visible light with heterocumulenes. This method significantly advances conventional use electrophilic carbenes stabilized by metal catalysts and harsh reaction conditions. The was explored isocyanates, carbodiimides,

Язык: Английский

---

Research and Application of Pyridinium 1,4-Zwitterionic Thiolates in Organic Synthesis

Chinese Journal of Organic Chemistry, Год журнала: 2023, Номер 43(11), С. 3844 - 3844

Опубликована: Янв. 1, 2023

Язык: Английский

---