Twofold Radical-Based Synthesis of N,C-Difunctionalized Bicyclo[1.1.1]pentanes

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(26), С. 9729 - 9736

Опубликована: Июнь 23, 2021

Bicyclo[1.1.1]pentylamines (BCPAs) are of growing importance to the pharmaceutical industry as sp3-rich bioisosteres anilines and N-tert-butyl groups. Here we report a facile synthesis 1,3-disubstituted BCPAs using twofold radical functionalization strategy. Sulfonamidyl radicals, generated through fragmentation α-iodoaziridines, undergo initial addition [1.1.1]propellane afford iodo-BCPAs; newly formed C–I bond in these products is then functionalized via silyl-mediated Giese reaction. This chemistry also translates smoothly iodo-BCPs. A wide variety acceptors iodo-BCPAs accommodated, providing straightforward access an array valuable aniline-like isosteres.

Язык: Английский

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A metal-free route to alkynyl sulfones under photoinduced conditions with the insertion of sulfur dioxide

Green Chemistry, Год журнала: 2020, Номер 22(6), С. 1906 - 1910

Опубликована: Янв. 1, 2020

A metal-free route to alkynyl sulfones under photoinduced conditions is accomplished, starting from 4-alkyl Hantzsch esters, sulfur dioxide, and bromides visible light irradiation at room temperature.

Язык: Английский

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Alkyl Carbazates for Electrochemical Deoxygenative Functionalization of Heteroarenes

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(27), С. 10859 - 10863

Опубликована: Март 30, 2020

The C-O bond cleavage for activation of alcohols is synthetically useful and practically challenging. This work describes carbazate as a new type electrochemically activated alkylating agent derived from ubiquitous direct functionalization heteroarenes under mild electrolytic conditions. simple undivided cell at low oxidative potentials with carbon/platinum electrode set-ups offers excellent substrate tolerance, affording variety primary, secondary tertiary alkyl-decorated heterocycles in good chemical yields. Furthermore, the mechanism this electrochemical deoxyalkylation reaction has been investigated.

Язык: Английский

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TsCl-promoted sulfonylation of quinoline N-oxides with sodium sulfinates in water

Chinese Chemical Letters, Год журнала: 2019, Номер 30(12), С. 2287 - 2290

Опубликована: Авг. 5, 2019

Язык: Английский

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Alkyl/Glycosyl Sulfoxides as Radical Precursors and Their Use in the Synthesis of Pyridine Derivatives**

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(31)

Опубликована: Июнь 1, 2022

We report here the use of simple and readily available alkyl sulfoxides as precursors to radicals their application in preparation pyridine derivatives. show that sulfoxides, N-methoxy pyridinium salts fluoride anions form electron donor-acceptor (EDA) complexes solution, which, upon visible light irradiation, undergo a radical chain process afford various derivatives smoothly. This reaction displays broad scope with respect both pyridiniums. The synthetic versatility handle chemistry adds power precursors. Glycosyl are converted corresponding pyridyl C-glycosides high stereoselectivities. Computational experimental studies provide insights into mechanism.

Язык: Английский

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Super-Reducing Behavior of Benzo[b]phenothiazine Anion Under Visible-Light Photoredox Condition

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(41), С. 22403 - 22412

Опубликована: Окт. 3, 2023

Herein we describe the anion of benzo[b]phenothiazine as a super reductant species upon excitation by visible light. In contrary to N-substituted phenothiazines or benzophenothiazines, this molecule holds extreme reducing power promote single electron transfer-based reductive cleavage at potential -3.51 V vs SCE. As proof, plethora aryl chloride substrates have been reductively cleaved fabricate molecules class isoindolinone and oxindole. Moreover, an aryl-chloride bond has homolytically generate radicals that utilized for C-C cross-coupling C-P formation reactions. To prove its ability, some fluoride bonds radicals. A detailed photophysical study including steady-state time-resolved spectroscopic techniques explain molecule's behavior light excitation, correlates with reactivity pattern. Theoretical calculations disclose benzophenothiazine be slightly puckered ground state is antiaromatic in nature. contrast, excited-state geometry planar, which also close intermediate after one transfer. Abating antiaromaticity anionic partially responsible highly behavior.

Язык: Английский

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Generation and Application of Aryl Radicals Under Photoinduced Conditions

Chemistry - A European Journal, Год журнала: 2024, Номер 30(31)

Опубликована: Март 28, 2024

Abstract Photoinduced aryl radical generation is a powerful strategy in organic synthesis that facilitates the formation of diverse carbon‐carbon and carbon‐heteroatom bonds. The synthetic applications photoinduced complex compounds, including natural products, physiologically significant molecules, functional materials, have received immense attention. An overview current developments production methods their uses given this article. A generalized idea how to choose reagents approach for radicals described, along with techniques associated mechanistic insights. Overall, article offers critical assessment results as well selection reaction parameters specific context cascades, cross‐coupling reactions, functionalization, selective C−H functionalization substrates.

Язык: Английский

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Recent advances in the direct β-C(sp²)–H functionalization of enamides

Organic & Biomolecular Chemistry, Год журнала: 2020, Номер 18(8), С. 1504 - 1521

Опубликована: Янв. 1, 2020

Recent advances in the direct β-C(sp²)–H functionalization of enamides, mainly including arylation, alkenylation, alkynylation, alkylation, acylation, sulfonylation, phosphorylation, and others, are reported.

Язык: Английский

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A copper-catalyzed insertion of sulfur dioxide via radical coupling

Chemical Communications, Год журнала: 2020, Номер 56(21), С. 3225 - 3228

Опубликована: Янв. 1, 2020

A copper-catalyzed reaction of O-acyl oximes, DABCO·(SO₂)₂, and 2H-azirines is developed under mild conditions, leading to diverse tetrasubstituted β-sulfonyl N-unprotected enamines with excellent stereoselectivity regioselectivity.

Язык: Английский

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Clean preparation of S-thiocarbamates with in situ generated hydroxide in 2-methyltetrahydrofuran

Chinese Chemical Letters, Год журнала: 2019, Номер 30(12), С. 2259 - 2262

Опубликована: Июнь 28, 2019

Язык: Английский

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