Recent Advances in the Functionalization of Terminal and Internal Alkynes

Asian Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 11(5)

Published: March 9, 2022

Abstract Alkynes are one of the most fundamental and diverse functional groups utilized in organic synthesis. Over past few years, development efficient synthetic methodologies for functionalization alkynes has been an active area research. A plethora alkyne reactions have reported literature to construct functionalized alkene scaffolds, which important building blocks many natural products, pharmaceuticals, key intermediates various transformations. In this review, we describe recent advances with emphasis on substrate scope, limitations, regioselectivity control applications these reactions. This review covers from 2016 2021.

Language: Английский

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Iridium‐Catalyzed Hydrochlorination and Hydrobromination of Alkynes by Shuttle Catalysis

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(7), P. 2904 - 2910

Published: Nov. 26, 2019

Described herein are two different methods for the synthesis of vinyl halides by a shuttle catalysis based iridium-catalyzed transfer hydrohalogenation unactivated alkynes. The use 4-chlorobutan-2-one or tert-butyl halide as donors hydrogen allows this transformation in absence corrosive reagents, such acid chlorides, thus largely improving functional-group tolerance and safety profile these reactions compared to state-of-the-art. This method has granted access alkenyl compounds containing acid-sensitive groups, tertiary alcohols, silyl ethers, acetals. synthetic value those methodologies been demonstrated gram-scale where low catalyst loading was achieved.

Language: Английский

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A fruitful century for the scalable synthesis and reactions of biphenyl derivatives: applications and biological aspects

RSC Advances, Journal Year: 2023, Volume and Issue: 13(27), P. 18262 - 18305

Published: Jan. 1, 2023

This review provides recent developments in the current status and latest synthetic methodologies of biphenyl derivatives.

Language: Английский

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Regio- and Stereoselective Synthesis of 1,2-Dihaloalkenes Using In-Situ-Generated ICl, IBr, BrCl, I2, and Br2

Chem, Journal Year: 2020, Volume and Issue: 6(4), P. 1018 - 1031

Published: April 1, 2020

Language: Английский

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Decarbonylative Transfer Hydrochlorination of Alkenes and Alkynes Based on a B(C₆F₅)₃‐Initiated Grob Fragmentation

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(24)

Published: March 25, 2022

Readily available cyclohexa-2,5-dien-1-ylcarbonyl chloride derivatives are introduced as bench-stable HCl surrogates for transfer hydrochlorination of terminal and internal alkenes well selected alkynes. The stepwise Grob fragmentation those acyl chlorides into chloride, carbon monoxide, a low-molecular-weight arene, proton is promoted by B(C6 F5 )3 . This decarbonylative process enables the addition across C-C double triple bonds with Markovnikov selectivity at room temperature.

Language: Английский

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Ionic Transfer Reactions with Cyclohexadiene-Based Surrogates

Synlett, Journal Year: 2019, Volume and Issue: 30(20), P. 2216 - 2232

Published: Nov. 6, 2019

A current research program in our laboratory is devoted to the development of cyclohexa-1,4-diene-based surrogates difficult-to-handle compounds and their application metal-free ionic transfer reactions. These investigations grew from interest silylium ion chemistry consequently concentrated initially on gaseous explosive hydrosilanes such as Me3SiH even monosilane (SiH4). Since then, we have expanded concept design other species including H2, mineral acids (HI HBr), hydrocarbons (isobutane isobutene). This Account summarizes discoveries this area date, describing challenges faced along way how combatted them. 1 Introduction 2 Transfer Hydrofunctionalization: Variation Electrofuge 3 Nucleofuge 4 Hydrohalogenation Using a Modified Surrogate 5 Synthesis 6 Conclusion

Language: Английский

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Regiodivergent DH or HD Addition to Alkenes: Deuterohydrogenation versus Hydrodeuterogenation

Organic Letters, Journal Year: 2020, Volume and Issue: 22(4), P. 1628 - 1632

Published: Feb. 11, 2020

The regioselective and regiodivergent addition of H-D to a variety 1,1-diarylalkenes was realized utilizing selectively deuterated dihydroaromatic compounds, which were generated by cobalt catalysis. reaction initiated catalytic amounts BF3·Et2O abstracting hydride or deuteride ions from the respective reducing agents led highly incorporation deuterium hydrogen at desired positions starting material.

Language: Английский

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Indium‐Catalysed Transfer Hydrogenation for the Reductive Cyclisation of 2‐Alkynyl Enones towards Trisubstituted Furans

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(44), P. 23661 - 23666

Published: Sept. 3, 2021

Indium tribromide catalysed the transfer hydrogenation from dihydroaromatic compounds, such as commercially available γ-terpinene, to enones, which resulted in cyclisation trisubstituted furan derivatives. The reaction was initiated by a Michael addition of hydride nucleophile enone subunit followed Lewis-acid-assisted and formation furan-indium intermediate Wheland derived starting material. product formed protonation complex replaced indium substituent. In addition, site-specific deuterium labelling HD surrogates site specific products gave useful insights into mechanism H-D scrambling.

Language: Английский

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Indium Tribromide‐Catalysed Transfer‐Hydrogenation: Expanding the Scope of the Hydrogenation and of the Regiodivergent DH or HD Addition to Alkenes

Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 27(43), P. 11221 - 11225

Published: May 28, 2021

Abstract The transfer‐hydrogenation as well the regioselective and regiodivergent addition of H−D from regiospecific deuterated dihydroaromatic compounds to a variety 1,1‐di‐ trisubstituted alkenes was realised with InBr 3 in dichloro(m)ethane. In comparison previously reported BF ⋅Et 2 O‐catalysed process, electron‐deficient aryl‐substituents can be applied reliably thereby several restrictions could lifted, new types substrates transformed successfully hydrodeuterogenation deuterohydrogenation reactions.

Language: Английский

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Photo‐Induced Halogen‐Atom Transfer: Generation of Halide Radicals for Selective Hydrohalogenation Reactions

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(43)

Published: May 25, 2022

The first photo-mediated process enabling the generation of halide radicals by Halogen-Atom Transfer (XAT) is described. Contrary to radical transformations involving XAT reactivity, which exploit stable carbon radicals, this unique approach uses 1,2-dihaloethanes for unstable XAT. These transient then undergo β-scission with release ethylene and formation more have been used in selective hydrohalogenations a large number unsaturated hydrocarbons, including Michael acceptors, unactivated alkenes alkynes. This hydrohalogenation tolerant broad range functionalities believed proceed through radical-chain manifold that propagates use silane derivatives.

Language: Английский

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