Thioether-Directed C4-Selective C–H Acylmethylation of Indoles Using α-Carbonyl Sulfoxonium Ylides

Organic Letters, Journal Year: 2020, Volume and Issue: 22(12), P. 4806 - 4811

Published: June 1, 2020

Site-selective direct functionalization of an indole benzenoid core has been a great challenge due to its inherently poor reactivity. We herein demonstrate iridium-catalyzed C4-selective acylmethylation indoles using α-carbonyl sulfoxonium ylides as carbene precursors. This method exhibits high efficiency and broad functional group compatibility. The directing was easily removed or converted other functionalities after the catalysis. potential synthetic utility coupling products highlighted by constructing medium-sized polycyclic indoles.

Language: Английский

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Rh(III)-Catalyzed Reaction of α-Carbonyl Sulfoxonium Ylides and Alkenes: Synthesis of Indanones via [4 + 1] Cycloaddition

Organic Letters, Journal Year: 2020, Volume and Issue: 22(4), P. 1375 - 1379

Published: Feb. 3, 2020

The synthesis of indanone derivatives by the Rh(III)-catalyzed reaction α-carbonyl sulfoxonium ylides with activated alkenes is reported. shows a high tolerance for functional groups and furnishes variety substituted via formal [4 + 1] cycloaddition. Highly stable were used as substrates in this C-H functionalization, their bifunctional character could be effectively exploited using Rh(III) catalysis sequential double C-C bond formation. Based on mechanistic studies including deuterium-labeling experiments, proposed to proceed follows: oxidative alkenylation β-hydride elimination, readdition H-Rh species, 1,2-carbon shift elimination DMSO, protonation.

Language: Английский

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Divergent Synthesis of Tetrasubstituted Phenols via [3 + 3] Cycloaddition Reaction of Vinyl Sulfoxonnium Ylides with Cyclopropenones

Organic Letters, Journal Year: 2023, Volume and Issue: 25(23), P. 4286 - 4291

Published: June 2, 2023

Two categories of tetrasubstituted phenols were prepared via the cycloaddition reaction vinyl sulfoxonnium ylides with cyclopropenones in a switchable manner. Copper carbenoid was proposed as active intermediate process 2,3,4,5-tetrasubstituted formation, while 2,3,5,6-tetrasubstituted generated direct [3 + 3] annulation under metal-free conditions. Further synthetic applications also demonstrated.

Language: Английский

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Synthesis of α-Carbonyl-α′-amide Sulfoxonium Ylides from Isocyanates with Complete Atom Economy

Organic Letters, Journal Year: 2023, Volume and Issue: 25(7), P. 1214 - 1217

Published: Feb. 9, 2023

An efficient catalyst- and additive-free facile synthesis of α-carbonyl-α′-amide sulfoxonium ylides from isocyanates β-ketosulfoxonium with complete atom economy has been described. The adorned various functional groups were well-tolerated afforded moderate to high yields the ylide derivatives. Finally, using large-scale reactions converting synthesized into other valuable compounds, we demonstrated practicality this synthetic method.

Language: Английский

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A Platform for the Synthesis of Diverse Phosphonyl and Thiofunctionalized Sulfoxonium Ylides

Organic Letters, Journal Year: 2024, Volume and Issue: 26(27), P. 5811 - 5816

Published: June 28, 2024

A practical strategy for the construction of diverse phosphonyl and thiofunctionalized sulfoxonium ylides via controllable monofunctionalization hybrid I(III)/S(VI) is presented. This process allows efficient P–H insertion under Cu catalysis, enabling synthesis ylides, whereas reaction with sulfur-containing reagents including AgSCF3, KSC(S)OR, KSCN mild conditions resulted in α-trifluoromethylthiolation, dithiocarbanation, thiocyanation accordingly. Of note, wide substrate compatibility (108 examples), excellent efficiency (up to 99% yield), gram-scale experiments, various product derivatizations highlight synthetic utility this protocol.

Language: Английский

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Synthesis of Furoxans and Isoxazoles via Divergent [2 + 1 + 1 + 1] Annulations of Sulfoxonium Ylides and ^tBuONO

Organic Letters, Journal Year: 2019, Volume and Issue: 21(13), P. 5273 - 5276

Published: June 26, 2019

We have presented a simple and new method for the divergent assembly of furoxans isoxazoles in which [2 + 1 1] annulation reaction sulfoxonium ylides is reported first time. When was performed using tBuONO as nitrogen source without metal catalyst, desired were obtained decent yields with wide substrate scope. Isoxazoles bearing three carbonyl groups achieved when conducted Cu(TFA)2 catalyst.

Language: Английский

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Metal-Free Chemoselective Reaction of Sulfoxonium Ylides and Thiosulfonates: Diverse Synthesis of 1,4-Diketones, Aryl Sulfursulfoxonium Ylides, and β-Keto Thiosulfones Derivatives

Organic Letters, Journal Year: 2020, Volume and Issue: 22(16), P. 6600 - 6604

Published: Aug. 10, 2020

A diverse chemoselective insertion reaction of sulfoxonium ylides and thiosulfonates under transition-metal-free conditions is developed, which successfully affords 1,4-diketone compounds, arylthiosulfoxide-ylides, β-keto thiosulfones, respectively. The nucleophilic addition two molecular to construct sulfone-substituted 1,4-dione compounds the highlight this work.

Language: Английский

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Direct Access to 1,1-Dicarbonyl Sulfoxonium Ylides from Aryl Halides or Triflates: Palladium-Catalyzed Carbonylation

Organic Letters, Journal Year: 2019, Volume and Issue: 21(13), P. 5310 - 5314

Published: June 26, 2019

The synthesis of 1,1-dicarbonyl sulfoxonium ylides by palladium-catalyzed carbonylation aryl halides or triflates with α-carbonyl has been developed for the first time. This method provides a general approach to synthetically useful in high efficiency. protocol displays wide substrate scope, showing that resulting have converted into corresponding 1,3-dicarbonyl compounds.

Language: Английский

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Elemental Sulfur-Mediated Synthesis of Quinoxalines from Sulfoxonium Ylides

Organic Letters, Journal Year: 2023, Volume and Issue: 25(28), P. 5329 - 5332

Published: July 7, 2023

A novel straightforward and catalyst-free approach for synthesizing quinoxaline derivatives from sulfoxonium ylides o-phenylenediamines mediated by elemental sulfur has been described. Due to the simple mild reaction conditions, decorated with different functional groups furnished moderate high yields of were well tolerated. Finally, large-scale reactions, synthesis pyrazines, some bioactive compounds are used illustrate potential utility developed approach.

Language: Английский

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Rh(III)‐Catalyzed Diverse C—H Functionalization of Iminopyridinium Ylides

Chinese Journal of Chemistry, Journal Year: 2021, Volume and Issue: 39(9), P. 2489 - 2494

Published: May 9, 2021

Main observation and conclusion Divergent synthesis of useful skeletons has been realized via rhodium(III)‐catalyzed C—H activation iminopyridinium ylides coupling with various unsaturated reagents. Isocoumarins isoquinolones were obtained cleavage the C—N or N—N bond in ylidic directing group, while fluorinated alkenes delivered group intact. The reactions occurred wide substrate scopes good efficiency under redox‐neutral air‐tolerant conditions. Representative products exhibit solid‐state fluorescent property bioactivity inhibition toward human cancer cells.

Language: Английский

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