Synlett, Год журнала: 2024, Номер unknown
Опубликована: Дек. 2, 2024
Abstract An indium-catalyzed cyanomethylation of α-alkynyl α,β-unsaturated ketones with 3-azido-2-methylbut-3-en-2-ol is presented. Furan-substituted propanenitriles were produced in yields 29–97%. The reaction involves a nucleophile addition/cycloisomerization process.
Язык: Английский
Angewandte Chemie International Edition, Год журнала: 2020, Номер 60(5), С. 2355 - 2363
Опубликована: Окт. 22, 2020
Abstract The regio‐ and enantioselective (3+3) cycloaddition of nitrones with 2‐indolylmethanols was accomplished by the cooperative catalysis hexafluoroisopropanol (HFIP) chiral phosphoric acid (CPA). Using this approach, a series indole‐fused six‐membered heterocycles were synthesized in high yields (up to 98 %), excellent enantioselectivities 96 % ee ) exclusive regiospecificity. This approach enabled not only first organocatalytic asymmetric but also C3‐nucleophilic 2‐indolylmethanols. More importantly, theoretical calculations elucidated role cocatalyst HFIP helping CPA control reactivity enantioselectivity reaction, demonstrating new mode catalysis.
Язык: Английский
Процитировано
104
Accounts of Chemical Research, Год журнала: 2020, Номер 53(10), С. 2358 - 2371
Опубликована: Окт. 1, 2020
ConspectusA small-molecule collection with structural diversity and complexity is a prerequisite to using either drug candidates or chemical probes for discovery chemical–biology investigations, respectively. Over the past 12 years, we have engaged in developing efficient diversity-oriented cascade strategies synthesis of topologically diverse skeletons incorporating biologically relevant motifs such as O- N-heterocycles, fused polycycles, multifunctionalized allenes. In particular, highlighted use simple, linear, densely functionalized molecular platforms these reactions.This account details our efforts design novel metal- organo-catalyzed reactions, which include 2-(1-alknyl)-2-alken-1-ones (yne–enones) heterocyclization/cross-coupling cascades, heterocyclization/cycloaddition nucleophilic addition/cross-coupling addition/heterocyclization so on. Moreover, this Account outlines corresponding mechanistic insights, computational information, applications cascades construction various highly substituted carbo- heterocycles well acyclic compounds, e.g., allenes dienes. addition yne–enones, evolved functional groups original yne–enones provide series yne–enone variants, resulted products complementary reactivities.The reactivity profile defined by presence an alkyne moiety conjugated enone unit their mutual through-bond connectivity. Owing conceptually rapid development carbophilic activation, identified catalytic systems consisting metal catalysts, including Pd, Au, Rh complexes, catalysis, allowing unprecedented reactions be achieved through different-types reaction intermediates, all-carbon 1,n-dipoles, furan-based o-quinodimethanes (oQDMs), allenyl-metal species. commonly known transition-metal activity, Lewis acidity complexes crucial accomplish transformation. addition, enantioselective gold(I)-catalyzed variants were application bisphosphines (e.g., Cn-TunePhos), monophosphines, developed "Ming–Phos" chiral ligands. Importantly, Ming–Phos ligands exhibited excellent performance gold-catalyzed mechanistically distinct [3 + n]-cycloaddition sulfinamide possibly responsible interaction substrate control enantioselectivity. Subsequently, demonstrated that easily prepared polymer-supported ligand could applied heterogeneously asymmetric cycloaddition good stereocontrol. With metal-free divergent functionalization provides numerous synthetic outlets structure diversification. For example, are particularly attractive precursors achiral heterocycles, pyrazoles, isoxazoles, pyrroles, pyrans, etc.
Язык: Английский
Процитировано
95
Chemistry - An Asian Journal, Год журнала: 2021, Номер 16(5), С. 364 - 377
Опубликована: Янв. 2, 2021
Asymmetric gold catalysis has been rapidly developed in the past ten years. Breakthroughs have made by rational design and meticulous selection of chiral ligands. This review summarizes newly gold-catalyzed enantioselective organic transformations recent progress ligand (since 2016), organized according to different types ligands, including bisphosphine monophosphine phosphite-derived N-heterocyclic carbene ligands for asymmetric gold(I) as well heterocyclic oxazoline gold(III) catalysis.
Язык: Английский
Процитировано
73
ChemPlusChem, Год журнала: 2021, Номер 86(9), С. 1283 - 1296
Опубликована: Июль 12, 2021
Abstract Gold(I) catalysts are ideal for the activation of alkynes under very mild conditions. However, unlike allenes or alkenes, triple bond cannot be prochiral. In addition, linear coordination displayed by gold(I) complexes places chiral ligand far away from substrate resulting in an inefficient transfer information. This poses a significant challenge achievement high enantiocontrol gold(I)‐catalyzed reactions alkynes. Although considerable progress on enantioselective transformations has recently been achieved, asymmetric non‐prochiral alkyne‐containing small molecules still represents great challenge. Herein we summarize recent advances intra‐ and intermolecular involving alkynes, discussing new designs that lie at basis these developments. We also focus mode action catalysts, their possible limitations towards next‐generation more efficient designs. Finally, square planar gold(III) complexes, which offer alternative to discussed.
Язык: Английский
Процитировано
55
New Journal of Chemistry, Год журнала: 2021, Номер 45(26), С. 11420 - 11456
Опубликована: Янв. 1, 2021
The 1,3-dipolar cycloaddition reaction of nitrone is one the most important methods for synthesis different sizes heterocycles which have enormous applications in natural products, biologically active molecules and pharmaceuticals.
Язык: Английский
Процитировано
49
ACS Catalysis, Год журнала: 2022, Номер 12(7), С. 4046 - 4053
Опубликована: Март 16, 2022
Gold(I) complexes of a chiral phosphoric acid-functionalized phosphine the CPA-Phos series enable enantioselective multicomponent reactions between aldehydes, hydroxylamines and cyclic yne-enones, leading to 3,4-dihydro-1H-furo[3,4-d][1,2]oxazines. This represents rare example highly reaction in gold(I) catalysis. The proceed at low catalyst loading provide high yields, total diastereoselectivity, enantiomeric excesses up 99%. Silver-free conditions can be applied. method has very broad scope as it applies both aliphatic aromatic aldehydes hydroxylamines, variety yne-enone-derived oximes. DFT calculations complement this study enlighten reactivity issues mechanistic pathways.
Язык: Английский
Процитировано
39
Russian Chemical Bulletin, Год журнала: 2024, Номер 73(1), С. 53 - 109
Опубликована: Янв. 1, 2024
Язык: Английский
Процитировано
8
Organic & Biomolecular Chemistry, Год журнала: 2020, Номер 18(40), С. 7977 - 7986
Опубликована: Янв. 1, 2020
2-Activated 1,3-enyne has emerged as a versatile synthetic precursor for the construction of valuable enantioenriched molecules.
Язык: Английский
Процитировано
50
Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(13), С. 3307 - 3312
Опубликована: Янв. 1, 2023
An unprecedented example of skeletal editing pyrrolidines to 1,2-oxazinanes expands the applicability scope “single-atom” skeletal-editing technologies.
Язык: Английский
Процитировано
15
Organic Letters, Год журнала: 2025, Номер unknown
Опубликована: Май 12, 2025
Herein, we report a gold(I)-catalyzed heterocyclization/(5 + 3) cycloaddition cascade of yne-enones with imidazolidines, providing modular, atom-economical and efficient strategy for the synthesis cycloocta[c]furans in moderate to excellent yields. This method features readily available substrates, simple operation, mild reaction conditions, broad substrate scope. More importantly, asymmetric version is also achieved by employing (R)-C2-TunePhos ligand (L7), leading optically active up 98:2 er.
Язык: Английский
Процитировано
0