Chiral phosphoric acid-catalyzed asymmetric dearomatization reactions

Chemical Society Reviews, Год журнала: 2019, Номер 49(1), С. 286 - 300

Опубликована: Дек. 12, 2019

We summarize in this review the recent development of chiral phosphoric acid (CPA)-catalyzed asymmetric dearomatization reactions.

Язык: Английский

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Advances in Catalytic Asymmetric Dearomatization

ACS Central Science, Год журнала: 2021, Номер 7(3), С. 432 - 444

Опубликована: Фев. 22, 2021

Asymmetric catalysis has been recognized as the most enabling strategy for accessing chiral molecules in enantioenriched forms. Catalytic asymmetric dearomatization is an emerging and dynamic research subject catalysis, which received considerable attention recent years. The direct transformations from readily available aromatic feedstocks to structurally diverse three-dimensional polycyclic make catalytic reactions of broad interest both organic synthesis medicinal chemistry. However, inherent difficulty disruption aromaticity demands a large energy input during process, might be incompatible with conditions generally required by catalysis. In this Outlook, we will discuss representative strategies examples various compounds try convince readers that overcoming above obstacles, could advance chemical sciences many respects.

Язык: Английский

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Progresses in organocatalytic asymmetric dearomatization reactions of indole derivatives

Organic Chemistry Frontiers, Год журнала: 2020, Номер 7(23), С. 3967 - 3998

Опубликована: Янв. 1, 2020

This review summarizes the progresses in organocatalytic asymmetric dearomatization reactions of indole derivatives and their applications total synthesis natural products, gives some insights into challenging issues this research field.

Язык: Английский

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Shaping Molecular Landscapes: Recent Advances, Opportunities, and Challenges in Dearomatization

Chem, Год журнала: 2020, Номер 6(7), С. 1589 - 1603

Опубликована: Июль 1, 2020

Язык: Английский

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Indole Alkaloid Synthesis Facilitated by Photoredox Catalytic Radical Cascade Reactions

Accounts of Chemical Research, Год журнала: 2019, Номер 52(7), С. 1877 - 1891

Опубликована: Июль 2, 2019

The monoterpene indole alkaloids, containing over 3000 known members and more than 40 structural types, represent one of the largest natural product families that have proven to be an important drug source. Their complex chemical structures significant biological activities rendered these alkaloids attractive targets in synthetic community for decades. While chemists developed many methodologies tactics toward this end, general strategies allowing divergent access a large variety types are still limited highly desirable. Photoredox catalysis has emerged recent years as powerful tool realize transformations via single electron transfer (SET) processes would otherwise inaccessible. In particular, when radical species generated by visible light photoinduced approach is involved well-designed cascade reactions, formation multiple bonds assembly structurally molecules secured green economic manner. This protocol might serve remodel way thinking preparation useful pharmaceuticals products. Due long-standing interest synthesis diverse our group previously cyclopropanation strategy ( Qin , Y. Acc. Chem. Res. 2011 44 447 ) was versatile several intriguing alkaloid molecules. With idea developing approaches various possible, we recently disclosed new reactions enabled photoredox catalysis, leading collective asymmetric total 42 belonging 7 types. Several discoveries deserve highlighted. First, use photocatalytic technology allowed us achieve unusual reaction pathway reversed conventional reactivity between two nucleophilic amine enamine groups. Second, crucial nitrogen-centered radical, directly from sulfonamide N-H bond, triggered three deliver cores with manifold functionalities controllable diastereoselectivities. Moreover, expansion catalytic, scalable, methodology permitted collection alkaloids. Account, wish provide complete picture studies concerning original design, method development, applications synthesis. It anticipated visible-light-driven will find further utility realm

Язык: Английский

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Energy-Transfer-Enabled Dearomative Cycloaddition Reactions of Indoles/Pyrroles via Excited-State Aromatics

Accounts of Chemical Research, Год журнала: 2022, Номер 55(17), С. 2510 - 2525

Опубликована: Авг. 9, 2022

Exploring the enormous chemical space through an expedient building-up of molecular diversity is important goal organic chemistry. The development synthetic methods toward molecules with unprecedented structural motifs lays foundation for wide applications ranging from pharmaceutical chemistry to materials science. In this regard, dearomatization arenes has been recognized as a unique strategy since it provides novel retrosynthetic disconnections various spiro or fused polycyclic increased saturation and stereoisomerism. However, inherent thermodynamic challenges are associated processes. disruption aromaticity arene substrates usually requires large energy inputs, which makes harsh conditions necessary many ground-state reactions. Therefore, further expansion scope reactions remains major problem not fully solved in chemistry.The past decade witnessed tremendous progress on photocatalytic under visible light. Particularly, via transfer mechanism have unlocked new opportunities Mediated by appropriately chosen photosensitizers, aromatic can be excited. This kind precise input might make feasible some that otherwise unfavorable thermal because significant increases substrates. Nevertheless, lifetimes key intermediates energy-transfer-enabled reactions, such excited-state aromatics downstream biradical species, quite short. How regulate reactivities these transient achieve exclusive selectivity certain reaction pathway among possibilities crucial issue addressed.Since 2019, our group reported series visible-light-induced dearomative cycloaddition indole pyrrole derivatives. It was found units excited irradiation light presence suitable photosensitizer. These readily undergo [m + n] tethered unsaturated functionalities including alkenes, alkynes, N-alkoxy oximes, (hetero)arenes, vinylcyclopropanes. yield indolines pyrrolines highly strained small- and/or medium-sized rings embedded, possess bridge- cagelike topologies. Systematic mechanistic studies confirmed involvement process. Density functional theory (DFT) calculations revealed correlation between substrate structure excitation efficiency, accelerated optimization parameters. Meanwhile, DFT demonstrated competition kinetically thermodynamically controlled pathways open-shell singlet intermediates, allowed complete switches [2 2] 1,5-hydrogen atom oximes [4 naphthalene. Furthermore, ab initio dynamics (AIMD) simulations uncovered post-spin crossing dynamic effects, determine regioselectivity recombination step pyrrole-derived vinylcyclopropanes.An increasing number scientists joined research contributed more elegant examples area. mechanism, although still its infancy, exhibited great potential synthesis hardly accessed other methods. We believe future will push boundary find related disciplines.

Язык: Английский

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Aromatic π-Components for Enantioselective Heck Reactions and Heck/Anion-Capture Domino Sequences

Accounts of Chemical Research, Год журнала: 2022, Номер 55(5), С. 734 - 745

Опубликована: Фев. 4, 2022

ConspectusOlefin functionalization represents one of the most important synthetic transformations in organic synthesis. Over past decades, palladium-catalyzed enantioselective Heck reactions, and Heck/anion-capture domino sequences through olefin carbopalladation followed by termination resulting alkyl-Pd species have been extensively developed. Extension coupling partners from classical olefins to other π-components would enable further advances open new space this field. Aromatics are easily available bulk chemicals. Dearomative transformation endocyclic aromatic π-bonds via reaction pathway provides an efficient straightforward route structurally diverse alicyclic compounds. Nevertheless, major challenges for include aromaticity breaking reactivity selectivity issues.Recently, we engaged developing catalytic dearomative reactions related reactions. A range heteroarenes naphthalenes employed as novel π-coupling these Through migratory insertion C–C interception transient species, reductive difunctionalization heteroarenyne cycloisomerization established. Relying on β-H elimination intermediate, realized with a partners, including heterocyclic indoles, pyrroles, furans, benzofurans, more challenging carbocyclic naphthalenes. In order avoid utilization organohalide electrophiles, was developed merging intermolecular alkyne hydropalladation intramolecular reaction. Cycloisomerization alkyne-tethered indoles delivered chiral indolines excellent enantioselectivities 100% atom economy. On hand, were established nucleophilic trapping intermediate. When HCO2Na capturing reagent, realized. By employing nucleophiles, alkynes, N-sulfonylhydrazones, organoboron reagents, series Two vicinal stereocenters enantio- diastereoselectivities constructed corresponding Heck/Sonogashira, Heck/vinylation, Heck/borylation Moreover, 1,4-diarylation Heck/Suzuki which competitive C–H arylation direct Suzuki almost fully inhibited presence spiro-phosphoramidite ligand.In Account, provide panoramic view our results since 2015 extending systems. Investigations outlined Account access variety heteropolycyclic molecules starting simple planar

Язык: Английский

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Nickel‐Catalyzed Asymmetric Reductive Carbo‐Carboxylation of Alkenes with CO₂

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(25), С. 14068 - 14075

Опубликована: Апрель 1, 2021

Abstract Reductive carboxylation of organo (pseudo)halides with CO 2 is a powerful method to provide carboxylic acids quickly. Notably, the catalytic reductive carbo‐carboxylation unsaturated hydrocarbons via fixation highly challenging but desirable approach for structurally diverse acids. There are only few reports and no examples alkenes transition metal catalysis. We report first asymmetric nickel A variety aryl (pseudo)halides, such as bromides, triflates inert chlorides particular note, undergo reaction smoothly give important oxindole‐3‐acetic acid derivatives bearing C3‐quaternary stereocenter. This transformation features mild conditions, wide substrate scope, facile scalability, good excellent chemo‐, regio‐ enantioselectivities. The highlights formal synthesis (−)‐Esermethole, (−)‐Physostigmine (−)‐Physovenine, total (−)‐Debromoflustramide B, (−)‐Debromoflustramine B (+)‐Coixspirolactam A; thereby, opening an avenue chiral natural products .

Язык: Английский

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Asymmetric dearomatization catalysed by chiral Brønsted acids via activation of ynamides

Nature Chemistry, Год журнала: 2021, Номер 13(11), С. 1093 - 1100

Опубликована: Окт. 11, 2021

Язык: Английский

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Intermolecular Formal Cycloaddition of Indoles with Bicyclo[1.1.0]butanes by Lewis Acid Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(48)

Опубликована: Авг. 16, 2023

Abstract Herein, we develop a new approach to directly access architecturally complex polycyclic indolines from readily available indoles and bicyclo[1.1.0]butanes (BCBs) through formal cycloaddition promoted by commercially Lewis acids. The reaction proceeded stepwise pathway involving nucleophilic addition of BCBs followed an intramolecular Mannich form rigid indoline‐fused structures, which resemble indole alkaloids. This tolerated wide range BCBs, thereby allowing the one‐step construction various indoline polycycles containing up four contiguous quaternary carbon centers.

Язык: Английский

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