Achieving Site-Selectivity for C–H Activation Processes Based on Distance and Geometry: A Carpenter’s Approach

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(24), P. 10571 - 10591

Published: May 21, 2020

The ability to differentiate between highly similar C–H bonds in a given molecule remains fundamental challenge organic chemistry. In particular, the lack of sufficient steric and electronic differences located distal functional groups has prevented development site-selective catalysts with broad scope. An emerging approach circumvent this obstacle is utilize distance target bond coordinating group, along geometry cyclic transition state directed activation, as core molecular recognition parameters multiple bonds. Perspective, we discuss advent recent advances concept. We cover wide range transition-metal-catalyzed, template-directed remote activation reactions alcohols, carboxylic acids, sulfonates, phosphonates, amines. Additionally, review eminent examples which take advantage non-covalent interactions achieve regiocontrol. Continued advancement distance- geometry-based differentiation for regioselective functionalization may lead ultimate realization editing: freedom modify molecules at any site, order.

Language: Английский

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Introduction: CH Activation

Chemical Reviews, Journal Year: 2017, Volume and Issue: 117(13), P. 8481 - 8482

Published: July 12, 2017

ADVERTISEMENT RETURN TO ISSUEEditorialNEXTIntroduction: CH ActivationRobert H. Crabtree and Aiwen LeiView Author Information Yale University Wuhan UniversityCite this: Chem. Rev. 2017, 117, 13, 8481–8482Publication Date (Web):July 12, 2017Publication History Published online12 July 2017Published inissue 12 2017https://pubs.acs.org/doi/10.1021/acs.chemrev.7b00307https://doi.org/10.1021/acs.chemrev.7b00307editorialACS PublicationsCopyright © 2017 American Chemical Society. This publication is available under these Terms of Use. Request reuse permissions free to access through this site. Learn MoreArticle Views39442Altmetric-Citations261LEARN 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 by 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 (2 MB) Get e-AlertscloseSUBJECTS:Alcohols,Functionalization,Hydrocarbons,Metals,Palladium e-Alerts

Language: Английский

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sp³ C–H Arylation and Alkylation Enabled by the Synergy of Triplet Excited Ketones and Nickel Catalysts

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(38), P. 12200 - 12209

Published: Sept. 5, 2018

Triplet ketone sensitizers are of central importance within the realm photochemical transformations. Although radical-type character triplet excited states diaryl ketones suggests viability for triggering hydrogen-atom transfer (HAT) and single-electron (SET) processes, among others, their use as multifaceted catalysts in C–C bond-formation via sp3 C–H functionalization alkane feedstocks still remains rather unexplored. Herein, we unlock a modular platform forging C(sp3)–C(sp2) C(sp3)–C(sp3) linkages from abundant bonds functional handles using synergy between nickel simple, cheap ketones. This method is distinguished by its wide scope that obtained starting precursors, thus complementing existing inner-sphere protocols or recent photoredox scenarios based on iridium polypyridyl complexes. Additionally, such provides new strategy streamlining synthesis complex molecules with high levels predictable site-selectivity preparative utility. Mechanistic experiments suggest abstraction occurs HAT state. We believe this study will contribute to more systematic utilization metallaphotoredox scenarios.

Language: Английский

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Late‐Stage Peptide Diversification by Position‐Selective C−H Activation

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(45), P. 14700 - 14717

Published: July 3, 2018

The late-stage modification of structurally complex peptides bears great potential for drug discovery, crop protection, and the pharmaceutical industry, among others. Whereas traditional approaches largely rely on prefunctionalizations, C-H activation catalysis has in recent years emerged as an increasingly powerful tool post-translational peptide modifications a step-economic manner. Herein, we summarize progress organometallic until June 2018, including position- chemoselective palladium-, ruthenium-, manganese-catalyzed processes.

Language: Английский

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Methodologies and Strategies for Selective Borylation of C–Het and C–C Bonds

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(15), P. 7348 - 7398

Published: June 29, 2020

Organoborons have emerged as versatile building blocks in organic synthesis to achieve molecular diversity and carboxylic acid bioisosteres with broad applicability drug discovery. Traditionally, these compounds are prepared by the substitution of Grignard/lithium reagents electrophilic boron species Brown hydroboration. Recent developments provided new routes for efficient preparation organoborons applying reactions using chemical feedstocks leaving groups. As compared previous methods that used halides (I, Br, Cl), direct borylation less reactive C–Het C–C bonds has become highly important get efficiency functional-group compatibility. This Review aims provide a comprehensive overview this topic, including (1) C–F bond borylation, (2) C–O (3) C–S (4) C–N (5) borylation. Considerable attention is given strategies mechanisms involved. We expect will inspire chemists discover more transformations expand field.

Language: Английский

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