HFIP in Organic Synthesis

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(15), P. 12544 - 12747

Published: July 17, 2022

1,1,1,3,3,3-Hexafluoroisopropanol (HFIP) is a polar, strongly hydrogen bond-donating solvent that has found numerous uses in organic synthesis due to its ability stabilize ionic species, transfer protons, and engage range of other intermolecular interactions. The use this exponentially increased the past decade become choice some areas, such as C–H functionalization chemistry. In review, following brief history HFIP an overview physical properties, literature examples reactions using or additive are presented, emphasizing effect each reaction.

Language: Английский

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Sulfoxonium ylides: simple compounds with chameleonic reactivity

Organic & Biomolecular Chemistry, Journal Year: 2020, Volume and Issue: 18(43), P. 8793 - 8809

Published: Jan. 1, 2020

Sulfur ylides first disclosed in 1930 started to gain more attention the 1960s, thanks mainly studies by Corey and Chaykovsky on their use for preparation of strained rings. More recently, chemistry these compounds has experienced important growth, part due similarity reactivities with diazo compounds. This short review provides an overview great assortment reactions sulfoxonium ylides, outlining a comparison between congeners: sulfonium Insertion reactions, cyclisation ring-opening are highlighted, giving particular catalytic asymmetric methodologies.

Language: Английский

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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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Traceless directing groups: a novel strategy in regiodivergent C–H functionalization

Chemical Communications, Journal Year: 2020, Volume and Issue: 56(83), P. 12479 - 12521

Published: Jan. 1, 2020

The use of functional groups as internal ligands for assisting C-H functionalization, termed the chelation assisted strategy, is emerging one most powerful tools construction C-C and C-X bonds from inert bonds. However, there are various directing which cannot be either removed after functionalization or require some additional steps reagents their removal, thereby limiting scope structural diversity products, step atom economy system. These limitations overcome by traceless group (TDG) strategy wherein substrate removal can carried out in a pot fashion. Traceless serve ideal with high degree reactivity selectivity without any requirement removal. present review overviews such carboxylic acids, aldehydes, N-oxides, nitrones, N-nitroso amines, amides, sulfoxonium ylides silicon tethered transition metal catalyzed reactions last decade.

Language: Английский

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Application of sulfoxonium ylide in transition-metal-catalyzed C-H bond activation and functionalization reactions

Tetrahedron, Journal Year: 2021, Volume and Issue: 101, P. 132478 - 132478

Published: Oct. 8, 2021

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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Ruthenium(IV) Intermediates in C−H Activation/Annulation by Weak O‐Coordination

Chemistry - A European Journal, Journal Year: 2018, Volume and Issue: 24(62), P. 16548 - 16552

Published: Sept. 25, 2018

Abstract Ruthenium(IV) complexes were identified as key intermediates of C−H/O−H activations by weak O ‐coordination. Thus, the annulations sulfoxonium ylides benzoic acids provided expedient access to diversely‐decorated isocoumarins with ample scope. Detailed experimental and computational studies strong support for a facile BIES‐C−H activation, along cyclometalated ruthenium(IV) within versatile ruthenium(II/IV) catalysis regime (BIES=base‐assisted internal electrophilic substitution).

Language: Английский

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Iridium-catalyzed B–H insertion of sulfoxonium ylides and borane adducts: a versatile platform to α-boryl carbonyls

Chemical Communications, Journal Year: 2019, Volume and Issue: 56(3), P. 423 - 426

Published: Dec. 4, 2019

Iridium-catalyzed boron-hydrogen bond insertion reactions of trimethylamine-borane and sulfoxonium ylides have been demonstrated, furnishing α-boryl ketones in moderate to excellent yields most cases (51 examples; up 84%). This practical scalable reaction showed broad substrate scope, high functional-group compatibility could be applied late-stage modification structurally complex drug compounds. Further synthetic applications were also demonstrated.

Language: Английский

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Chemospecific Cyclizations of α‐Carbonyl Sulfoxonium Ylides on Aryls and Heteroaryls

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(45), P. 16198 - 16202

Published: Sept. 11, 2019

The functionalization of aryl and heteroaryls using α-carbonyl sulfoxonium ylides without the help a directing group has remained so far neglected area, despite advantageous safety profile ylides. Described herein are cyclizations onto benzenes, benzofurans N-p-toluenesulfonyl indoles in presence base HFIP, whereas pyrroles N-methyl undergo cyclization an iridium catalyst. Significantly, these two sets conditions chemospecific for each groups substrates.

Language: Английский

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Enantioselective S−H Insertion Reactions of α‐Carbonyl Sulfoxonium Ylides

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(36), P. 15554 - 15559

Published: April 30, 2020

Abstract The first example of enantioselective S−H insertion reactions sulfoxonium ylides is reported. Under the influence thiourea catalysis, excellent levels enantiocontrol (up to 95 % ee ) and yields 97 %) are achieved for 31 examples in aryl thiols α‐carbonyl ylides.

Language: Английский

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