Activation of C–O and C–N Bonds Using Non-Precious-Metal Catalysis

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(20), P. 12109 - 12126

Published: Sept. 10, 2020

ADVERTISEMENT RETURN TO ISSUEPREVViewpointNEXTActivation of C–O and C–N Bonds Using Non-Precious-Metal CatalysisTimothy B. BoitTimothy BoitDepartment Chemistry Biochemistry, University California, Los Angeles, California 90095, United StatesMore by Timothy Boit, Ana S. BulgerAna BulgerDepartment Bulger, Jacob E. DanderJacob DanderDepartment Dander, Neil K. Garg*Neil GargDepartment States*E-mail: [email protected]More Garghttp://orcid.org/0000-0002-7793-2629Cite this: ACS Catal. 2020, 10, 20, 12109–12126Publication Date (Web):September 2020Publication History Received30 July 2020Published online10 September inissue 16 October 2020https://pubs.acs.org/doi/10.1021/acscatal.0c03334https://doi.org/10.1021/acscatal.0c03334article-commentaryACS PublicationsCopyright © 2020 American Chemical Society. This publication is available under these Terms Use. Request reuse permissions free to access through this site. Learn MoreArticle Views15643Altmetric-Citations116LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum full text article downloads since November 2008 (both PDF HTML) across all institutions individuals. These metrics regularly updated reflect usage leading up last few days.Citations number other articles citing article, calculated Crossref daily. Find more information about citation counts.The Altmetric Attention Score a quantitative measure attention that research has received online. Clicking on donut icon will load page at altmetric.com with additional details score social media presence for given article. how calculated. Share Add toView InAdd Full Text ReferenceAdd Description ExportRISCitationCitation abstractCitation referencesMore Options onFacebookTwitterWechatLinked InRedditEmail (3 MB) Get e-AlertscloseSUBJECTS:Alkyls,Amides,Coupling reactions,Cross coupling reaction,Organic compounds e-Alerts

Language: Английский

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Multicomponent Synthesis of α-Branched Amines via a Zinc-Mediated Carbonyl Alkylative Amination Reaction

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 9045 - 9062

Published: March 15, 2024

Methods for the synthesis of α-branched alkylamines are important due to their ubiquity in biologically active molecules. Despite development many methods amine preparation, C(sp3)-rich nitrogen-containing compounds continue pose challenges synthesis. While carbonyl reductive amination (CRA) between ketones and is cornerstone method alkylamine synthesis, it sometimes limited by sterically demanding condensation step dialkyl amines more restricted availability compared aldehydes. We recently reported a "higher-order" variant this transformation, alkylative (CAA), which utilized halogen atom transfer (XAT)-mediated radical mechanism, enabling streamlined complex alkylamines. efficacy visible-light-driven approach, displayed scalability issues, competitive was problem certain substrate classes, limiting applicability. Here, we report change reaction regime that expands CAA platform through realization an extremely broad zinc-mediated reaction. This new strategy enabled elimination CRA, simplified purification, improved scope. Furthermore, harnessed carboxylic acid derivatives as alkyl donors facilitated α-trialkyl tertiary amines, cannot be accessed via CRA. Zn-mediated can carried out at variety scales, from 10 μmol setup microtiter plates high-throughput experimentation, gram-scale medicinally-relevant compounds. believe transformation enables robust, efficient, economical access provides viable alternative current benchmark methods.

Language: Английский

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Site-Selective Copper(I)-Catalyzed Hydrogenation of Amides

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 3, 2025

We present a bifunctional catalyst consisting of copper(I)/N-heterocyclic carbene and an organocatalytic guanidine moiety that enables, for the first time, copper(I)-catalyzed reduction amides with H2 as terminal reducing agent. The allows reactivity tuning originally weakly nucleophilic copper(I) hydrides – formed in situ to be able react difficult-to-reduce amides. Additionally, is key selective recognition "privileged" based on simple readily available heterocycles presence other within one molecule, giving rise hitherto unknown site-selective catalytic amide hydrogenation. A substrate scope, mechanistic investigations, working hypothesis supported by computational analysis site-selectivity are presented.

Language: Английский

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Site-Selective α-C–H Functionalization of Trialkylamines via Reversible Hydrogen Atom Transfer Catalysis

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(45), P. 18952 - 18959

Published: Nov. 5, 2021

Trialkylamines are widely found in naturally occurring alkaloids, synthetic agrochemicals, biological probes, and especially pharmaceuticals agents preclinical candidates. Despite the recent breakthrough of catalytic alkylation dialkylamines, selective α-C(sp3)–H bond functionalization available trialkylamine scaffolds holds promise to streamline complex synthesis, accelerate drug discovery, execute late-stage pharmaceutical modification with complementary reactivity. However, canonical methods always result at less-crowded site. Herein, we describe a solution switch reaction site through fundamentally overcoming steric control that dominates such processes. By rapidly establishing an equilibrium between α-amino C(sp3)–H bonds highly electrophilic thiol radical via reversible hydrogen atom transfer, leverage slower radical-trapping step electron-deficient olefins selectively forge C(sp3)–C(sp3) more-crowded radical, overall selectivity guided by Curtin–Hammett principle. This subtle profile has unlocked new strategic concept direct C–H arena for forging C–C from diverse set trialkylamines high levels preparative utility. Simple correlation 13C NMR shift serves as qualitative predictive guide. The broad consequences this dynamic system, together ability N-substituted quaternary carbon centers implement techniques, hold potential synthesis small-molecule discovery.

Language: Английский

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Enantioselective Reductive Cyanation and Phosphonylation of Secondary Amides by Iridium and Chiral Thiourea Sequential Catalysis

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(16), P. 8827 - 8831

Published: Jan. 23, 2021

The combination of transition-metal catalysis and organocatalysis increasingly offers chemists opportunities to realize diverse unprecedented chemical transformations. By combining iridium with chiral thiourea catalysis, direct enantioselective reductive cyanation phosphonylation secondary amides have been accomplished for the first time synthesis enantioenriched α-aminonitriles α-aminophosphonates. protocol is highly efficient enantioselective, providing a novel route optically active α-functionalized amines from simple, readily available feedstocks. In addition, reactions are scalable catalyst can be recycled reused.

Language: Английский

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Deoxygenative Functionalizations of Aldehydes, Ketones and Carboxylic Acids

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 61(10)

Published: Nov. 15, 2021

The simple and efficient conversion of carbonyl compounds into functionalized alkanes via deoxygenation is highly enabling in chemical synthesis. This Review covers the recent methodology development carboxyl deoxygenative functionalizations, highlighting some representative significant contributions this field. These advances are categorized based on reactivity patterns oxygenated feedstock compounds, including aldehydes, ketones carboxylic acids. Four types reactive intermediates arising from aldehydes during deoxygenation, namely, bis-electrophiles, carbenoids, bis-nucleophiles alkyl radical equivalents, presented, while acids mainly behave as tris-electrophiles when deoxygenated. In each subcategory, selected examples organized according to type bond formation discussed a generalized mechanistic perspective.

Language: Английский

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Challenges and Breakthroughs in Selective Amide Activation

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(49)

Published: Sept. 20, 2022

In contrast to ketones and carboxylic esters, amides are classically seen as comparatively unreactive members of the carbonyl family, owing their unique structural electronic features. However, recent decades have emergence research programmes focused on selective activation under mild conditions. past four years, this area has continued rapidly develop, with new advances coming in at a fast pace. Several novel strategies been demonstrated effective tools for amide activation, enabling transformations that once synthetically useful mechanistically intriguing. This Minireview comprises field, highlighting trends breakthroughs what could be called age activation.

Language: Английский

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Recent advances in visible light-induced C(sp3)–N bond formation

Nature Reviews Chemistry, Journal Year: 2022, Volume and Issue: 6(8), P. 544 - 561

Published: July 11, 2022

Language: Английский

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Total Syntheses of Calyciphylline A-Type Alkaloids (−)-10-Deoxydaphnipaxianine A, (+)-Daphlongamine E and (+)-Calyciphylline R via Late-Stage Divinyl Carbinol Rearrangements

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(35), P. 16042 - 16051

Published: Aug. 25, 2022

Among the famous Daphniphyllum alkaloids family, calyciphylline A-type subfamily has triggered particular interest from organic synthesis community in recent years. Here, we report divergent total syntheses of three alkaloids, namely, (−)-10-deoxydaphnipaxianine A, (+)-daphlongamine E, and (+)-calyciphylline R. Our work highlights an efficient, strategy via late-stage divinyl carbinol rearrangements, including unprecedented oxidative Nazarov electrocyclization using unfunctionalized tertiary unusual allylic alcohol rearrangement. A highly efficient "donor–acceptor" platinum catalyst was used for a critical nitrile hydration step. Moreover, power selective amide reductions also been showcased by novel classic tactics.

Language: Английский

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Catalytic enantioselective reductive alkynylation of amides enables one-pot syntheses of pyrrolidine, piperidine and indolizidine alkaloids

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Oct. 6, 2023

The primary objective in synthetic organic chemistry is to develop highly efficient, selective, and versatile methodologies, which are essential for discovering new drug candidates agrochemicals. In this study, we present a unified strategy one-pot, catalytic enantioselective synthesis of α-alkyl α,α'-dialkyl pyrrolidine, piperidine, indolizidine alkaloids using readily available amides alkynes. This enabled by the identification development an Ir/Cu/N-PINAP catalyzed chemoselective reductive alkynylation α-unbranched aliphatic amides, serves as key reaction. reaction combined with Pd-catalyzed tandem reactions one-pot approach, enabling collective, total syntheses eight anticancer antipode 90-98% ee. methodology's enantio-divergence exemplified one-step access either enantiomer alkaloid bgugaine.

Language: Английский

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