Catalytic asymmetric dearomatization (CADA) reaction-enabled total synthesis of indole-based natural products

Natural Product Reports, Год журнала: 2019, Номер 36(11), С. 1589 - 1605

Опубликована: Янв. 1, 2019

The recent enantioselective total syntheses of natural products enabled by catalytic asymmetric dearomatization reactions indole derivatives are presented.

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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Selective Arene Hydrogenation for Direct Access to Saturated Carbo‐ and Heterocycles

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(31), С. 10460 - 10476

Опубликована: Янв. 31, 2019

Arene hydrogenation provides direct access to saturated carbo- and heterocycles thus its strategic application may be used shorten synthetic routes. This powerful transformation is widely applied in industry expected facilitate major breakthroughs the sciences. The ability overcome aromaticity while controlling diastereo-, enantio-, chemoselectivity central use of preparation complex molecules. In general, multisubstituted arenes yields predominantly cis isomer. Enantiocontrol imparted by chiral auxiliaries, Brønsted acids, or transition-metal catalysts. Recent studies have demonstrated that highly chemoselective transformations are possible. Such methods underlying strategies reviewed herein, with an emphasis on synthetically useful examples employ readily available

Язык: Английский

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Visible-light induced dearomatization reactions

Chemical Society Reviews, Год журнала: 2022, Номер 51(6), С. 2145 - 2170

Опубликована: Янв. 1, 2022

This review provides an overview of visible-light induced dearomatization reactions classified based on the manner in which aromaticity is disrupted.

Язык: Английский

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Photochemical intermolecular dearomative cycloaddition of bicyclic azaarenes with alkenes

Science, Год журнала: 2021, Номер 371(6536), С. 1338 - 1345

Опубликована: Март 25, 2021

Heteroaromatics lured into cycloadditions The Diels-Alder reaction is widely used to produce six-membered carbon rings from alkenes and dienes. such as quinolines resemble dienes in principle, but practice their pairs of double bonds are inert toward because aromatic stabilization. Ma et al. report that by using an iridium photosensitizer, they could excite related azaarenes triplet states, thereby disrupting the aromaticity enabling intermolecular, Diels-Alder–like reactivity (see Perspective Schmidt). reactions proceeded exclusively at flanking carbons outside nitrogen-containing ring. Science , this issue p. 1338 ; see also 1313

Язык: Английский

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Birch‐Type Photoreduction of Arenes and Heteroarenes by Sensitized Electron Transfer

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(40), С. 14289 - 14294

Опубликована: Авг. 5, 2019

The direct reduction of arenes and heteroarenes by visible-light irradiation remains challenging, as the energy a single photon is not sufficient for breaking aromatic stabilization. Shown herein that accumulation two photons allows dearomatization heteroarenes. Mechanistic investigations confirm combination energy-transfer electron-transfer processes generates an arene radical anion, which subsequently trapped hydrogen-atom transfer finally protonated to form dearomatized product. photoreduction converts planar feedstock compounds into molecular skeletons are use in organic synthesis.

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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Scaffold hopping by net photochemical carbon deletion of azaarenes

Science, Год журнала: 2022, Номер 376(6592), С. 527 - 532

Опубликована: Апрель 28, 2022

Discovery chemists routinely identify purpose-tailored molecules through an iterative structural optimization approach, but the preparation of each successive candidate in a compound series can rarely be conducted manner matching their thought process. This is because many necessary chemical transformations required to modify cores straightforward fashion are not applicable complex contexts. We report method that addresses one facet this problem by allowing hop directly between chemically distinct heteroaromatic scaffolds. Specifically, we show selective photolysis quinoline

Язык: Английский

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Hexadehydro-Diels–Alder Reaction: Benzyne Generation via Cycloisomerization of Tethered Triynes

Chemical Reviews, Год журнала: 2021, Номер 121(4), С. 2413 - 2444

Опубликована: Янв. 25, 2021

The hexadehydro-Diels–Alder (HDDA) reaction is the thermal cyclization of an alkyne and a 1,3-diyne to generate benzyne intermediate. This then rapidly trapped, in situ, by variety species yield highly functionalized benzenoid products. In contrast nearly all other methods aryne generation, no reagents are required produce HDDA benzyne. versatile customizable nature process has attracted much attention due not only its synthetic potential but also because fundamental mechanistic insights studies often afford. authors have attempted provide here comprehensive compilation publications appearing mid-2020 that describe experimental results reactions.

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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