Asymmetric transformations from sulfoxonium ylides

Chemical Science, Journal Year: 2021, Volume and Issue: 13(5), P. 1192 - 1209

Published: Dec. 8, 2021

Sulfoxonium ylides are important surrogates for diazo compounds, and their use in industry as safer alternatives has been evaluated during recent years. Beyond the known classical transformations, these have also used a surprising plethora of novel intrinsic chemical reactions, especially Bench stability handling an advantage this class organosulfur molecules. Despite this, efficient asymmetric specifically catalytic enantioselective versions, only recently reported, there specific reasons this. This perspective article covers topic from first studies up to latest advances, giving personal perspectives showing main challenges area coming

Language: Английский

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Recent Advances in Metal‐Catalyzed C−H Bond Functionalization Reactions of Sulfoxonium Ylides

Asian Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 11(4)

Published: March 23, 2022

Abstract In recent years, the transition‐metal‐catalyzed functionalization reactions of sulfoxonium ylides have been explored extensively because their usefulness as carbene‐transfer agents, since they can produce metal carbenes through catalysis. Moreover, are safer and advantages simple handling good stability over other counterparts like diazo‐compounds. This review article attempts to highlight advances in metal‐catalyzed C−H ylides.

Language: Английский

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Chameleonic Reactivity of Imidoyl Sulfoxonium Ylides: Access to Functionalized Pyrroles and Dihydro-pyridines

Organic Letters, Journal Year: 2024, Volume and Issue: 26(1), P. 62 - 67

Published: Jan. 3, 2024

We have found a chameleonic reactivity of imidoyl sulfoxonium ylides. On the one hand, ylides react with electron-deficient reagents, such as alkynyl esters, to lead formation 1,2-dihydro-pyridines. The methyl group attached sulfur atom acts methylene donor. other pyridinium 1,4-zwitterionic thiolates, which leads functionalized pyrroles. Both transformations feature mild reaction conditions and good functional tolerance.

Language: Английский

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Bidirectional Iterative Approach to Sequence-Defined Unsaturated Oligoesters

JACS Au, Journal Year: 2023, Volume and Issue: 3(1), P. 252 - 260

Published: Jan. 3, 2023

Herein, we describe the development of a new strategy for synthesis unsaturated oligoesters via sequential metal- and reagent-free insertion vinyl sulfoxonium ylides into O-H bond carboxylic acid. Like two directional coupling amino acids (N- to C-terminal C- N-terminal) in peptide synthesis, present approach offers both directions synthesize oligoesters. The addition ylide (acid iteration sequence) one direction (ylide another yield (Z)-configured To perform this iteration, have developed highly regioselective X-H (X = O, N, C, S, halogen) acids, thiols, phenols, amines, indoles, halogen under metal-free reaction conditions. is applied broad range substrates (>50 examples, up 99% yield) eight iterative sequences. Mechanistic studies suggest that rate-limiting step depends on type insertion.

Language: Английский

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Visible-Light-Promoted Synthesis of 1,3-Dicarbonyl Sulfoxonium Ylides

Organic Letters, Journal Year: 2022, Volume and Issue: 24(35), P. 6386 - 6390

Published: Aug. 26, 2022

A novel visible-light-promoted coupling of diazoketones with sulfoxonium ylides, employing a violet light-emitting diode, is described under both batch and continuous flow conditions. This transformation permits the direct synthesis synthetically useful 1,3-dicarbonyl ylides (33 examples, 21-85% yields), by means an acylation from in situ selective generation ketenes. The reaction performed conditions proved to be very efficient, providing higher yields shorter times.

Language: Английский

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Catalytic Asymmetric P–H Insertion Reactions

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(36), P. 20031 - 20040

Published: Aug. 29, 2023

Albeit notable endeavors in enantioselective carbene insertion into X–H bonds (X = C, O, N, S, Si, B), the catalytic asymmetric P–H reactions still stand for a long-lasting challenge. By merging transition-metal catalysis with organocatalysis, we achieve scalable transformation between diazo pyrazoleamides and H-phosphine oxides that upon subsequent reduction delivers wide variety of optically active β-hydroxyl phosphine good yields high enantioselectivity. The achiral copper catalyst fosters carbenoid bond, while chiral cinchona alkaloid-derived organocatalyst controls outcome. Density functional theory (DFT) calculations further reveal chelates to organocatalyst, enhances its acidity, accordingly promotes proton transfer. Our work showcases potential combining organocatalysis realize elusive reactions.

Language: Английский

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Visible-Light-Induced Carbene Insertion into P–H Bonds between Acylsilanes and H-Phosphorus Oxides

Organic Letters, Journal Year: 2023, Volume and Issue: 25(13), P. 2338 - 2343

Published: March 28, 2023

An intriguing visible-light-induced strategy has been established for the P-H insertion reaction between acylsilanes and H-phosphorus oxides that, upon a subsequent acidic process, deliver wide variety of α-hydroxyphosphorus in good yields (up to 93% yield). The metal-free protocol represents unique example C-P bond formation through situ generation siloxycarbenes. This methodology features advantages operational simplicity, mild conditions, broad substrate scope, column free gram-scale synthesis.

Language: Английский

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Photochemical Reactions of Sulfur Ylides

Current Organic Chemistry, Journal Year: 2024, Volume and Issue: 28(13), P. 978 - 990

Published: May 6, 2024

Abstract: Photochemical reactions offer unparalleled opportunities to access elusive chemical pathways and develop innovative strategies for constructing complex molecules. Within organic synthesis, photochemical have become indispensable tools accessing molecular structures, such as pharmaceuticals natural products. The ability of sulfur ylides participate in these diverse processes has made them the synthetic chemist's toolbox. use transformations garnered significant attention chemistry community, they serve powerful intermediates several transformations. This review article presents a comprehensive overview mediated by ylides. Herein, we describe key aspects reactivity presence light. compounds can be classified into three categories: energy acceptors, electron donors, trapping reagents.

Language: Английский

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Perhaloacylation of α-Carbonyl Sulfoxonium Ylides

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 2, 2025

A mild and efficient protocol for the perhaloacylation of α-carbonyl sulfoxonium ylides has been developed. The commercially available perfluoro- perchloroacid anhydrides were used as acylating agents in catalyst- additive-free reactions to access α-carbonyl-α'-perhaloacyl high yields. reaction offers a simple method prepare valuable polyfluorinated organosulfur molecules.

Language: Английский

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Fused Furan Moieties from Enol-like Compounds and β-Keto Sulfoxonium Ylides Involving sp² C–H Activation and Concomitant Tandem C–O Annulation

Organic Letters, Journal Year: 2023, Volume and Issue: 25(24), P. 4493 - 4497

Published: June 9, 2023

An efficient and fascinating protocol has been devised for the preparation of fused furan moieties involving a Rh(II) catalyzed one-pot C–H activation/concomitant tandem annulation process, employing an enolic compound β-keto sulfoxonium ylide as reacting conjugates. The developed technique demands only Rh2(TFA)4 catalyst to proceed forward is devoid additional metallic or nonmetallic additives. skeletal transformation naphthoquinone highly decorated indolizines promising synthetic application.

Language: Английский

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