Ni-Catalyzed Enantioselective Reductive Diarylation of Activated Alkenes by Domino Cyclization/Cross-Coupling

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(39), P. 12364 - 12368

Published: Sept. 20, 2018

A Ni-catalyzed enantioselective reductive diarylation of activated alkenes by domino cyclizative/cross-coupling two aryl bromides is developed. This reaction proceeds under very mild conditions and shows broad substrate scope, without requiring the use preformed organometallic reagents. Moreover, this approach provides direct access to various bis-heterocycles bearing all-carbon quaternary centers in synthetically useful yields (up 81%) with excellent enantioselectivity (>30 examples, 90–99% ee).

Language: Английский

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Recent advances in multi-component reactions and their mechanistic insights: a triennium review

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(15), P. 4237 - 4287

Published: Jan. 1, 2021

This review summarizes the recent developments in MCRs, incorporating different strategies along with their mechanistic aspects.

Language: Английский

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First-Row d-Block Element-Catalyzed Carbon–Boron Bond Formation and Related Processes

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(21), P. 13238 - 13341

Published: Oct. 7, 2021

Organoboron reagents represent a unique class of compounds because their utility in modern synthetic organic chemistry, often affording unprecedented reactivity. The transformation the carbon–boron bond into carbon–X (X = C, N, and O) stereocontrolled fashion has become invaluable medicinal agrochemistry, natural products chemistry as well materials science. Over past decade, first-row d-block transition metals have increasingly widely used catalysts for formation bond, traditionally catalyzed by expensive precious metals. This recent focus on alternative enabled growth fundamental methods organoboron chemistry. review surveys current state-of-the-art use element-based bonds.

Language: Английский

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Highly Enantioselective Cross-Electrophile Aryl-Alkenylation of Unactivated Alkenes

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(18), P. 7637 - 7643

Published: April 19, 2019

Enantioselective cross-electrophile reactions remain a challenging subject in metal catalysis, and with respect to data, studies have mainly focused on stereoconvergent of racemic alkyl electrophiles. Here, we report an enantioselective aryl-alkenylation reaction unactivated alkenes. This method provides access number biologically important chiral molecules such as dihydrobenzofurans, indolines, indanes. The incorporated alkenyl group is suitable for further that can lead increase molecular diversity complexity. proceeds under mild conditions at room temperature, easily accessible pyrox ligand used afford products high enantioselectivity. synthetic utility this demonstrated by enabling the modification complex peptides, indometacin, steroids.

Language: Английский

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Three-Component, Interrupted Radical Heck/Allylic Substitution Cascade Involving Unactivated Alkyl Bromides

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(22), P. 10173 - 10183

Published: May 7, 2020

Developing efficient and selective strategies to approach complex architectures containing (multi)stereogenic centers has been a long-standing synthetic challenge in both academia industry. Catalytic cascade reactions represent powerful means of rapidly leveraging molecular complexity from simple feedstocks. Unfortunately, carrying out Heck-type involving unactivated (tertiary) alkyl halides remains an unmet owing unavoidable β-hydride elimination. Herein, we show that modular, practical, general palladium-catalyzed, radical three-component coupling can indeed overcome the aforementioned limitations through interrupted Heck/allylic substitution sequence mediated by visible light. Selective 1,4-difunctionalization 1,3-dienes, such as butadiene, achieved employing different commercially available nitrogen-, oxygen-, sulfur-, or carbon-based nucleophiles bromides (>130 examples, mostly >95:5 E/Z, >20:1 rr). Sequential C(sp3)–C(sp3) C–X (N, O, S) bonds have constructed efficiently with broad scope high functional group tolerance. The flexibility versatility strategy illustrated gram-scale reaction streamlined syntheses ether, sulfone, tertiary amine products, some which would be difficult access via currently established methods.

Language: Английский

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Enantioselective Dicarbofunctionalization of Unactivated Alkenes by Palladium‐Catalyzed Tandem Heck/Suzuki Coupling Reaction

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(41), P. 14653 - 14659

Published: Aug. 17, 2019

Abstract A highly enantioselective dicarbofunctionalization of unactivated alkenes was implemented by a Pd‐catalyzed asymmetric tandem Heck/Suzuki coupling reaction. This reaction represents the first example intramolecular cyclization/cross‐coupling olefin‐tethered aryl halides with alkyl‐, alkenyl‐ or arylboronic acids, and provides rapid access to number chiral compounds, such as dihydrobenzofurans, indolines, chromanes, indanes bearing quaternary stereocenter, in good yields excellent enantioselectivities. The practicality this validated modification biologically complex molecules peptides, piperitol, CB2 receptor agonists, etc. Moreover, synthesis two enantiomers can be easily realized simple change order steps sequence.

Language: Английский

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Nickel‐Catalyzed Asymmetric Reductive Arylalkylation of Unactivated Alkenes

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(20), P. 6722 - 6726

Published: March 20, 2019

Abstract Reported is an asymmetric reductive dicarbofunctionalization of unactivated alkenes. Under the catalysis a Ni/BOX system, various aryl bromides, incorporating pendant olefinic unit, were successfully reacted with array primary alkyl bromides in presence Zn as reductant, furnishing series benzene‐fused cyclic compounds bearing quaternary stereocenter high enantioselectivities. Notably, this reaction avoids use pregenerated organometallics and demonstrates tolerance sensitive functionalities. The preliminary mechanistic investigations reveal that Ni‐catalyzed proceeds cascade consisting migratory insertion cross‐coupling nickel(I)‐mediated intramolecular 5‐ exo cyclization enantiodetermining step.

Language: Английский

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

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(5), P. 734 - 745

Published: Feb. 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

Language: Английский

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Ni-Catalyzed Ligand-Controlled Regiodivergent Reductive Dicarbofunctionalization of Alkenes

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(27), P. 10282 - 10291

Published: June 24, 2021

Transition-metal-catalyzed dicarbofunctionalization of alkenes involving intramolecular Heck cyclization followed by intermolecular cross-coupling has emerged as a powerful engine for building heterocycles with sterically congested quaternary carbon centers. However, only exo-cyclization/cross-coupling products can be obtained; endo-selective cyclization/cross-coupling not been reported yet and still poses formidable challenge. We herein report the first example catalyst-controlled regiodivergent synthesis five- six-membered benzo-fused lactams bearing all-carbon Using chiral Pyrox- or Phox-type bidentate ligand, 5-exo cyclization/cross-couplings proceed favorably to produce indole-2-ones in good yields excellent regioselectivity enantioselectivities (up 98% ee). When C6-carboxylic acid-modified 2,2′-bipyridine was used 3,4-dihydroquinolin-2-ones were obtained through 6-endo-selective processes. This transformation is modular tolerant variety functional groups. The ligand rather than substrate structures precisely dictates pattern. Moreover, synthetic value this protocol demonstrated preparation biologically relevant molecules structural scaffolds.

Language: Английский

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

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(25), P. 14068 - 14075

Published: April 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 .

Language: Английский

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