Gold(I)-Catalyzed Asymmetric Heterocyclization/(5 + 3) Cycloaddition of Yne-enones with Imidazolidines: Access to Cycloocta[c]furan Frameworks DOI
Yuncheng Liu,

X.-Y. Liu,

Song Gao

и другие.

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

High-order dipolar annulations with metal-containing reactive dipoles DOI
Mao‐Mao Zhang,

Bao‐Le Qu,

Bin Shi

и другие.

Chemical Society Reviews, Год журнала: 2022, Номер 51(10), С. 4146 - 4174

Опубликована: Янв. 1, 2022

The advances on metal-catalysed high-order dipolar annulations were comprehensively summarized in this review. To further exploit the potential of unique annulation strategy, a research outlook was also proposed.

Язык: Английский

Процитировано

89

Yne–Enones Enable Diversity-Oriented Catalytic Cascade Reactions: A Rapid Assembly of Complexity DOI
Deyun Qian, Junliang Zhang

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

Recent Advances in the Development of Chiral Gold Complexes for Catalytic Asymmetric Catalysis DOI
Jia‐Jun Jiang, Man‐Kin Wong

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

Asymmetric Dearomatization of Indole by Palladium/PC‐Phos‐Catalyzed Dynamic Kinetic Transformation DOI
Haoke Chu, Jie Cheng, Junfeng Yang

и другие.

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(49), С. 21991 - 21996

Опубликована: Сен. 2, 2020

Abstract A palladium‐catalyzed intermolecular dynamic kinetic asymmetric dearomatization of 3‐arylindoles with internal alkynes was developed the use achiral Xantphos and chiral sulfinamide phosphine ligand ( PC‐Phos ) as co‐ligands. This method could deliver various spiro[indene‐1,3′‐indole] compounds in good yields (up to 95 % yield) up 98 ee . The salient features transformation include readily available substrates, ease scale‐up versatile functionalization products. mechanistic experiments gave some insights on active intermediates.

Язык: Английский

Процитировано

72

Palladium/TY-Phos-Catalyzed Asymmetric Heck/Tsuji–Trost Reaction of o-Bromophenols with 1,3-Dienes DOI

Youshao Tu,

Bing Xu, Qian Wang

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(8), С. 4378 - 4383

Опубликована: Фев. 16, 2023

2,3-Dihydrobenzofurans are crucial building blocks in the synthesis of natural products and pharmaceutical molecules. However, their asymmetric has been a long-standing formidable challenge so far. In this work, we developed highly enantioselective Pd/TY-Phos-catalyzed Heck/Tsuji-Trost reaction o-bromophenols with various 1,3-dienes, allowing expedient access to chiral substituted 2,3-dihydrobenzofurans. This features excellent regio- enantiocontrol, high functional group tolerance, easy scalability. More importantly, demonstration method as valuable tool for construction optically pure (R)-tremetone fomannoxin is highlighted.

Язык: Английский

Процитировано

28

Asymmetric gold catalysis enabled by specially designed ligands DOI
Amol B. Gade,

Urvashi Urvashi,

Nitin T. Patil

и другие.

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(6), С. 1858 - 1895

Опубликована: Янв. 1, 2024

This review is planned to provide a comprehensive overview of the progress made in design and development chiral ligands for asymmetric gold catalysis.

Язык: Английский

Процитировано

13

Gold(I)‐Catalyzed Highly Diastereo‐ and Enantioselective Cyclization–[4+3] Annulation Cascades between 2‐(1‐Alkynyl)‐2‐alken‐1‐ones and Anthranils DOI
Rahul Dadabhau Kardile,

Tzu‐Hsuan Chao,

Mu‐Jeng Cheng

и другие.

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(26), С. 10396 - 10400

Опубликована: Март 25, 2020

This work reports gold-catalyzed [4+3]-annulations of 2-(1-alkynyl)-2-alken-1-ones with anthranils to yield epoxybenzoazepine products excellent exo-diastereoselectivity (dr>25:1). The utility this new gold catalysis is manifested by applicable substrates over a broad scope. More importantly, the enantioselective versions these [4+3]-cycloadditions have been developed satisfactorily chiral catalysts under ambient conditions (DCM, 0 °C); ee levels range from 88.0-99.9 %. With DFT calculations, we postulate stepwise pathway rationalize preferable exo-stereoselection.

Язык: Английский

Процитировано

65

New‐Generation Ligand Design for the Gold‐Catalyzed Asymmetric Activation of Alkynes DOI
Giuseppe Zuccarello, Imma Escofet,

Ulysse Caniparoli

и другие.

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

Asymmetric Cascade Cyclization of Enynamides with Photogenerated Ketenes via Relay Gold and N-Oxide Catalysis DOI
Dan Liŭ,

Zhen‐Cao Shu,

Zhihan Zhang

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(3), С. 1741 - 1749

Опубликована: Янв. 18, 2024

An asymmetric cascade cyclization of enynamides and α-diazoketones to produce chiral bicyclic lactams bearing all-carbon quaternary stereocenters is realized with up 95% yield, 98% ee, >19:1 dr. The combination visible light photoactivation the relay gold N-oxide catalysis in a process enabled facile generation controlled assembly two reactive intermediates, ketene aza-o-quinone methide. Theoretical calculations revealed stepwise [4 + 2] cycloaddition mechanism, stereochemistry by amide group catalyst. Remarkably, this study presents first example N-oxides serving as catalysts for illustrates how strategy could be promising means access significant heterocyclic scaffolds.

Язык: Английский

Процитировано

8

Base-Mediated [3 + 4]-Cycloaddition of Anthranils with Azaoxyallyl Cations: A New Approach to Multisubstituted Benzodiazepines DOI
Juan Feng,

Meng Zhou,

Xuanzi Lin

и другие.

Organic Letters, Год журнала: 2019, Номер 21(16), С. 6245 - 6248

Опубликована: Авг. 1, 2019

A new [3 + 4] cycloaddition of azaoxyallyl cations and anthranils has been achieved for rapid access to multisubstituted benzodiazepine derivatives. variety α-halo hydroxamates were both effective substrates with simple operations under transition-metal-free conditions. The intriguing features this method include its mild nature the reaction conditions, high efficiency, broad substrate scope, wide functional group compatibility.

Язык: Английский

Процитировано

52