Synthesis of β‐Keto Sulfones by Oxy‐Sulfonylation of Alkynes in HFIP

Chen, Xingyu; Lu, Sixian; Yan, Yuyan; Wang, Jigang; Liu, Yang; Sun, Peng

doi:10.1002/adsc.202101444

Cited by 11 publications

(1 citation statement)

References 67 publications

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“…In this case, pyridine played a vital role as base to effectively suppress H‐atom abstraction process of vinyl radical intermediate. [ 27 ] Later on, several different radical processes of alkynes with sulfonyl radical precursors mediated by varying catalysts, including photosensitizers (Ru(bpy) 3 ), [ 28 ] amino acids (histidine), [ 29 ] transition metals (Cu, Fe), [ 30‐31 ] electrochemical synthesis, [ 32 ] or promoted by special solvent (HFIP) [ 33 ] have been developed to solve the above‐mentioned issues (Scheme 1b). Despite these considerable improvements, homogeneous catalysts and harsh reaction conditions with unrecyclable metal salts, acids, bases, or utilization of excess oxidants greatly hinder their application from the viewpoint of green and sustainable synthetic…”

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confidence: 99%

Photocatalytic Aerobic Oxysulfonylation of Alkynes to Access β‐Keto Sulfones Catalyzed by OVs‐N‐Nb₂O₅

et al. 2022

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Herein, we report a novel heterogeneous photocatalyst for radical-mediated oxidative oxysulfonylation of alkynes to β-keto sulfones under environmentally benign conditions. The oxygen vacancy-rich semiconductor Nb 2 O 5 (labeled as OVs-N-Nb 2 O 5 ) could efficiently catalyze a wide range of alkynes, especially for those bearing electron-deficient substituents or internal alkynes, to their corresponding β-keto sulfones in good to high yields with good tolerance of diverse functional groups under visible-light illumination. The late-stage modification of steroidal compounds and synthesis of bioactive molecules were also achieved via this procedure, highlighting its potential for practical applications. Meanwhile, the photocatalyst OVs-N-Nb 2 O 5 showed outstanding catalytic stability for successive recycles without appreciable loss in activity and selectivity. The critical role of oxygen vacancies on improving reaction activity and selectivity was clearly disclosed via control experiments and theoretical calculation.

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Section: Background and Originality Contentmentioning

confidence: 99%

Photocatalytic Aerobic Oxysulfonylation of Alkynes to Access β‐Keto Sulfones Catalyzed by OVs‐N‐Nb₂O₅

et al. 2022

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HFIP‐Triggered Reduction Radical Coupling of Enamides with Alkynes Towards β‐Keto Alkylamides via H‐Bonding Electron Transfer

Cheng,

Zhao,

Yan

et al. 2024

ChemCatChem

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This study presents metal‐free protocols for the reduction radical coupling of enamides with diverse alkynes, triggered by 1,1,1,3,3,3‐Hexafluoro‐2‐propanol (HFIP), enabling access to β‐keto alkylamides. The established approach demonstrates remarkable efficiency, facile gram‐scale synthesis, and outstanding functional group tolerance. Mechanistic investigations have revealed that the radical reaction is initiated through H‐bonding electron transfer (Hb‐ET) between enamides and HFIP promoted by acids. Notably, the introduction of Hb‐ET protocols for generating radicals represents a highly promising approach in the field of radical chemistry.

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Synthesis of branched allylic sulfones by regioselective boron-catalysed hydrosulfonylation

et al. 2023

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Branched allylic sulfones are privileged scaffolds widely distributed in bioactive molecules, and organic functional materials. Some methods for the synthesis of allyl sulfones have been developed, such as Tsuji-Prost reaction, hydrosulfonylation and radical addition reactions. Despite these advances, the transition-metal-free hydrosulfonylation of unactive 1,3-diene leading to branched allylic sulfones has rarely explored.Herein, a boron-catalysed highly regioselective hydrosulfonylation of 1,3-diene with sul nic acid has been explored to construct a broad scope of branched allylic sulfones. The reactions proceed smoothly without the help of transition-metal-catalyst. Abundant structural motifs have also been obtained through simple transformation from the generated allylic sulfone products.Compared with the previous methods, this protocol exhibited advantages as following: 1) readily available starting material without pre-treatment; 2) under the catalysis of inexpensive boron tri uoride etherate, avoidance of transition-metal-catalyst; 3) simple operation and easy scale-up, and does not require dry conditions, an inert atmosphere or a water scavenger; 4) excellent atom economy and regioselectivity.

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Synthesis of β‐Keto Sulfones by Oxy‐Sulfonylation of Alkynes in HFIP

Cited by 11 publications

References 67 publications

Photocatalytic Aerobic Oxysulfonylation of Alkynes to Access β‐Keto Sulfones Catalyzed by OVs‐N‐Nb₂O₅

Photocatalytic Aerobic Oxysulfonylation of Alkynes to Access β‐Keto Sulfones Catalyzed by OVs‐N‐Nb₂O₅

HFIP‐Triggered Reduction Radical Coupling of Enamides with Alkynes Towards β‐Keto Alkylamides via H‐Bonding Electron Transfer

Synthesis of branched allylic sulfones by regioselective boron-catalysed hydrosulfonylation

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Synthesis of β‐Keto Sulfones by Oxy‐Sulfonylation of Alkynes in HFIP

Cited by 11 publications

References 67 publications

Photocatalytic Aerobic Oxysulfonylation of Alkynes to Access β‐Keto Sulfones Catalyzed by OVs‐N‐Nb2O5

Photocatalytic Aerobic Oxysulfonylation of Alkynes to Access β‐Keto Sulfones Catalyzed by OVs‐N‐Nb2O5

HFIP‐Triggered Reduction Radical Coupling of Enamides with Alkynes Towards β‐Keto Alkylamides via H‐Bonding Electron Transfer

Synthesis of branched allylic sulfones by regioselective boron-catalysed hydrosulfonylation

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Photocatalytic Aerobic Oxysulfonylation of Alkynes to Access β‐Keto Sulfones Catalyzed by OVs‐N‐Nb₂O₅

Photocatalytic Aerobic Oxysulfonylation of Alkynes to Access β‐Keto Sulfones Catalyzed by OVs‐N‐Nb₂O₅