Gold-Catalyzed Reactions of Specially Activated Alkynes, Allenes, and Alkenes

Chemical Reviews, Год журнала: 2020, Номер 121(14), С. 8756 - 8867

Опубликована: Ноя. 23, 2020

This review describes the gold-catalyzed reactions of specially activated alkynes, allenes, and alkenes. Such species are characterized by presence either electron-donating or electron-withdrawing groups as substituents carbon π-system. They intrinsically polarized, when compared to their nonspecially counterparts can therefore be involved in transformations featuring increased regio-, stereo-, chemoselectivities. The chemistry π-systems under homogeneous gold catalysis is extremely rich varied. reactivity observed with unsaturated systems often transposed ones without loss efficiency. However, also exhibit specific reactivities that cannot attained regular substrates. In this family π-systems, ynamides analogs, along alkynyl carbonyl derivatives, classes substrates have retained most attention. provides an overview developed all discussing general reactivities, presenting commenting on well applications.

Язык: Английский

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Homogeneous Gold-Catalyzed Oxidation Reactions

Chemical Reviews, Год журнала: 2021, Номер 121(14), С. 8979 - 9038

Опубликована: Фев. 16, 2021

Homogeneous gold catalysis has experienced extraordinary development since the dawn of this millennium. Oxidative is a vibrant and fertile subfield over years delivered diverse array versatile synthetic methods exceptional value to practices. This review aims cover topic in comprehensive manner. The discussions are organized by mechanistic aspects metal oxidation states further types oxidants or oxidizing functional groups. Synthetic applications oxidative also discussed.

Язык: Английский

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Calcium Carbide: Versatile Synthetic Applications, Green Methodology and Sustainability

European Journal of Organic Chemistry, Год журнала: 2020, Номер 2021(1), С. 43 - 52

Опубликована: Сен. 29, 2020

Acetylene is a key building block for organic chemistry and potentially can be involved in diverse range of synthetic transformations. However, critical analysis practical considerations showed that application gaseous acetylene regular labs encounters number difficulties. Safety limitations due to flammable explosive nature requirements specialized high‐pressure equipment impose serious drawbacks. Typical reaction conditions involve excess reactant, which simply released the atmosphere at end reaction, thus generating waste causing contamination. Calcium carbide brings new green sustainable wave into powerful alkyne transformations significantly expands repertoire traditional chemistry. The novel trend using calcium instead synthetically beneficial opens reactivity C≡C unit. This review highlights recent advances chemistry, demonstrates its advantages prospects term approach.

Язык: Английский

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Peptide Stapling by Crosslinking Two Amines with α‐Ketoaldehydes through Diverse Modified Glyoxal‐Lysine Dimer Linkers

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(16)

Опубликована: Фев. 20, 2024

α-Ketoaldehydes play versatile roles in the ubiquitous natural processes of protein glycation. However, leveraging reactivity α-ketoaldehydes for biomedical applications has been challenging. Previously, with guanidine harnessed to design probes labeling Arg residues on proteins an aqueous medium. Herein, a highly effective, broadly applicable, and operationally simple protocol stapling native peptides by crosslinking two amino groups through diverse imidazolium linkers various α-ketoaldehyde reagents is described. The use hexafluoroisopropanol as solvent facilitates rapid clean reactions under mild conditions enables unique selectivity Lys over Arg. naturally occurring GOLD/MOLD have expanded encompass wide range modified glyoxal-lysine dimer (OLD) linkers. In proof-of-concept trial, these modular enabled convenient two-round strategy streamline structure-activity relationship (SAR) study wasp venom peptide anoplin, leading enhanced biological activities.

Язык: Английский

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Gold‐Catalyzed Oxidative Alkyne Functionalization by N−O/S−O/C−O Bond Oxidants

Advanced Synthesis & Catalysis, Год журнала: 2020, Номер 362(18), С. 3664 - 3708

Опубликована: Май 11, 2020

Abstract Since the beginning of this century, homogeneous gold‐catalyzed alkyne transformations have been an active area research in pursuit developing efficient synthetic methodologies. This emerging which at exploited mild Lewis acid character gold and its propensity to form π‐complex with alkyne, has reinvigorated upon discovery oxidative functionalization 2007. The oxidation enabled direct access α‐oxo carbenes alkynal complex versatile reactivity applied achieve including but not limited oxyarylation, C−H, X−H (X=N, O) insertion, cyclization, cycloaddition, ring expansion, various cascade reactions. review provides a comprehensive summary methods, applications mechanistic insight by N−O/S−O/C−O bond oxidants covering literature reports appeared since magnified image

Язык: Английский

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Visible-Light-Induced Photocatalytic Oxidative Decarboxylation of Cinnamic Acids to 1,2-Diketones

The Journal of Organic Chemistry, Год журнала: 2021, Номер 86(9), С. 6486 - 6493

Опубликована: Апрель 14, 2021

A concerted metallophotoredox catalysis has been realized for the efficient decarboxylative functionalization of α,β-unsaturated carboxylic acids with aryl iodides in presence perylene bisimide dye to afford 1,2-diketones.

Язык: Английский

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The Dichotomy of Gold‐catalyzed Interplay between Cyanamides and Ynamides: Controllable Switch from [2+2+2] to [4+2] Cycloaddition

Advanced Synthesis & Catalysis, Год журнала: 2020, Номер 362(13), С. 2672 - 2682

Опубликована: Апрель 25, 2020

Abstract The gold‐catalyzed interplay between cyanamides and ynamides demonstrates condition‐dependent mechanistic dichotomy. [2+2+2] Cycloaddition proceeds under kinetically controlled conditions to give 2,4,6‐triaminopyrimidines (19 examples, up 99%). Under thermodynamically conditions, the reactivity switches from [2+2+2]‐ [4+2] cycloaddition; latter reaction accomplishes 1,3‐diaminoisoquinolines 97%). advantages of both methods include regioselectivity, mild (even for reaction) possibility introducing a variety dialkyl, diaryl, heterocyclic amino substituents into target pyrimidine isoquinoline cores. reactions were conducted on gram scales versatility obtained products was demonstrated by post‐functionalizations. magnified image

Язык: Английский

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Oxygen Atom Transfer as Key To Reverse Regioselectivity in the Gold(I)-Catalyzed Generation of Aminooxazoles from Ynamides

The Journal of Organic Chemistry, Год журнала: 2020, Номер 86(2), С. 1748 - 1757

Опубликована: Дек. 28, 2020

We report on gold(I)-catalyzed oxidative annulation involving ynamides, nitriles, and 2,3-dichloropyridine N-oxide. The application of N-oxide as an oxygen atom transfer reagent reverses the regioselectivity to give 5-amino-1,3-oxazoles, in comparison with previously reported syntheses aminooxazoles based gold-catalyzed nitrene transfers ynamides furnish 4-amino-1,3-oxazoles. developed approach allows generation 1,3-oxazoles containing a variety sulfonyl-protected alkylamino groups fifth position oxazole ring (29 examples; up 88% yields). In addition, use N-substituted namely cyanamides, leads facile difficult-to-obtain 2,5-diaminooxazoles. process is feasible for wide ranges or it can be conducted gram scale.

Язык: Английский

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New Reactions of Acetylene Generated in Two-Chamber Reactor

Russian Journal of General Chemistry, Год журнала: 2023, Номер 93(2), С. 235 - 239

Опубликована: Фев. 1, 2023

Язык: Английский

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DABCO-Catalyzed DMSO-Promoted Sulfurative 1,2-Diamination of Phenylacetylenes with Elemental Sulfur and o-Phenylenediamines: Access to Quinoxaline-2-thiones

Organic Letters, Год журнала: 2023, Номер 25(39), С. 7225 - 7229

Опубликована: Сен. 22, 2023

The oxidative amination of alkynes typically requires transition metal catalysts and strong oxidants. Herein, we alternatively utilize DABCO as a sulfur-activating catalyst to achieve the sulfurative 1,2-diamination phenylacetylenes with elemental sulfur o-phenylenediamines. DMSO was found be particularly suitable for use terminal oxidant this three-component process. A mechanistic study has shown that cascade reaction is triggered by addition active species triple bond phenylacetylenes.

Язык: Английский

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