Chemodivergent difunctionalization of alkenes through base-controlled radical relay

Shatskiy, Andrey; Alvey, Gregory R.; Kärkäs, Markus D.

doi:10.1016/j.chempr.2021.12.018

Cited by 7 publications

(2 citation statements)

References 9 publications

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“…Although some of these methods are useful, more effective protocols are still desired. In 1979, Naidan reported the thiocyanoarylsulfonylation of styrene with aryldiazo compounds, SO 2 and NH 4 SCN; recently, radical-based vicinal bifunctionalization of alkenes for synthesis of β-substituted sulfones, such as oxysulfonylation, sulfonoximation, hydroxysulfonylation, alkoxysulfonylation, halosulfonylation, aminosulfonyl-ation, and trifluoromethylchlorosulfonylation have been reported in the literature (Scheme a–c). Herein, we describe a general Mn(OAc) 3 -mediated thiocyanosulfonylation of alkenes (Scheme d).…”

Section: Introductionmentioning

confidence: 99%

Copper-Catalyzed Vicinal Thiocyanosulfonylation of Alkenes and Alkynes

Duan,

Xiao,

Ogundipe

et al. 2024

J. Org. Chem.

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Efficient copper-catalyzed radical thiocyanosulfonylation of alkenes and alkynes with potassium thiocyanate and sodium phenylsulfinate is described. The reactions provide general and convenient methods toward the synthesis of β-thiocyanoalkyl sulfones and β-thiocyanoalkenyl sulfones, respectively, in satisfactory yields. Based on conducted mechanistic experiments, a mechanism involving oxidative generation of sulfonyl radicals and subsequent addition to alkenes followed by Cu-assisted thiocyanation is proposed. Moreover, the practicability of the reaction is successfully demonstrated by its successful application on a gram scale.

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Section: Introductionmentioning

confidence: 99%

Copper-Catalyzed Vicinal Thiocyanosulfonylation of Alkenes and Alkynes

Duan,

Xiao,

Ogundipe

et al. 2024

J. Org. Chem.

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“…Typically, it was reviewed to synthesize 2,3-fused quinazolinones in a number of ways, including difunctionalization of alkenes, ring opening of easily available small rings, dehydrogenative cross-coupling reactions, transition-metal-catalyzed cyclizations, 4 + 2 or 4 + 1 cycloadditions, and other cascade reactions . In these methods, difunctionalization of olefins is usually initiated by free radicals through photoinduction or oxidation, followed by radical tandem addition and cyclization . Using this strategy, 2,3-fused five-membered rings and six membered-rings of quinazolones substituted with alkyl, fluoroalkyl, chloroalkyl, acyl, sulfonyl, nitrile, and hydroxyl groups were successfully synthesized.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of 2,3-Fused Quinazolinones via the Radical Cascade Pathway and Reaction Mechanistic Studies by DFT Calculations

et al. 2023

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An efficient radical cascade cyclization of unactivated alkenes toward the synthesis of a series of ring-fused quinazolinones has been developed in moderate to excellent yields using commercially available ethers, alkanes, and alcohols, respectively, under a base-free condition in a short time without a transition metal as catalyst. Notably, the transformations can be carried out with the advantages of a broad substrate scope and high atomic economy. Density functional theory calculations and wavefunction analyses were performed to elucidate the radical reaction mechanism.

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Predesign of Covalent‐Organic Frameworks for Efficient Photocatalytic Dehydrogenative Cross‐Coupling Reaction

Chen,

Sun,

Chen

et al. 2024

Advanced Materials

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The dehydrogenative cross‐coupling reaction is the premier route for synthesizing important 4‐quinazolinone drugs. However, it usually requires high reaction temperature and long reaction time, and the yield of the final product is low. Here two stable and photosensitive covalent‐organic frameworks (COFs), TAPP‐An and TAPP‐Cu‐An are purposefully designed and constructed to serve as unprecedented heterogeneous tandem catalysts to complete dehydrogenative cross‐coupling reactions in a short time and under mild reaction conditions (room temperature and light), leading to the high‐efficient photosynthesis of 4‐quinazolinones. Particularly, TAPP‐Cu‐An is the best heterogeneous catalyst currently available for the synthesis of 4‐quinazolinones, even surpassing all the catalysts reported so far. It also enables one‐step photosynthesis of 4‐quinazolinones with higher conversion (>99%) and selectivity (>99%) in a shorter time, and the product can be easily prepared on a gram scale. Extensive experiments combined with theoretical calculations show that the excellent photogenerated charge separation and transport capability, as well as the synergistic An‐Cu catalysis in TAPP‐Cu‐An are the main driving forces for this efficient reaction.

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Chemodivergent difunctionalization of alkenes through base-controlled radical relay

Cited by 7 publications

References 9 publications

Copper-Catalyzed Vicinal Thiocyanosulfonylation of Alkenes and Alkynes

Copper-Catalyzed Vicinal Thiocyanosulfonylation of Alkenes and Alkynes

Synthesis of 2,3-Fused Quinazolinones via the Radical Cascade Pathway and Reaction Mechanistic Studies by DFT Calculations

Predesign of Covalent‐Organic Frameworks for Efficient Photocatalytic Dehydrogenative Cross‐Coupling Reaction

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