Pd-catalysed C–H functionalisation of free carboxylic acids

Chemical Science, Год журнала: 2022, Номер 13(9), С. 2551 - 2573

Опубликована: Янв. 1, 2022

Pd-catalysed C–H functionalisation of free carboxylic acids has drawn significant attention over the last few years due to predominance acid moieties in pharmaceuticals and agrochemicals.

Язык: Английский

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Empirical Guidelines for the Development of Remote Directing Templates through Quantitative and Experimental Analyses

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(6), С. 2793 - 2803

Опубликована: Фев. 2, 2022

The ability to differentiate and selectively activate remote C-H bonds represents a perennial challenge in the field of activation. Since its first report 2012, now-established "directing template" (DT) approach remains demonstrably effective for functionalization bonds. As selectivity is hypothesized be principally determined by optimal positioning reactive catalyst target bond, DT's spatial factors are particularly important toward achieving high selectivity, though systematic study on requisite remain unelucidated. Through an in-depth analysis 119 structurally unique published DTs, this summarizes key that central at defined aryl positions, which experimentally corroborated through development new aliphatic meta para-selective DTs electronically unbiased arenes. These empirical rules, summarize distance geometric factors, expected useful tools future site-selective arene activation as well other reactions rely covalent/noncovalent DT-mediated regioselection.

Язык: Английский

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Ruthenium‐Catalyzed Stereo‐ and Site‐Selective ortho‐ and meta‐C−H Glycosylation and Mechanistic Studies

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(32)

Опубликована: Июнь 8, 2022

Abstract C‐aryl glycosides are popular basic skeletons in biochemistry and pharmaceutical chemistry. Herein, ruthenium‐catalyzed highly stereo‐ site‐selective ortho ‐ meta ‐C Ar −H glycosylation is described. A series of pyranosides furanosides were synthesized by this method. The strategy showed good substrate scope, various N ‐heterocyclic directing groups compatible with the reaction system. mechanistic study suggested that key pathway might involve oxidative addition/reduction elimination, whereas aryl ‐C−H was mediated σ ‐activation. Density functional theory calculations also high stereoselectivity due to steric hindrance.

Язык: Английский

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The green chemistry paradigm in modern organic synthesis

Russian Chemical Reviews, Год журнала: 2023, Номер 92(12), С. RCR5104 - RCR5104

Опубликована: Дек. 1, 2023

After the appearance of green chemistry concept, which was introduced in vocabulary early 1990s, its main statements have been continuously developed and modified. Currently, there are 10–12 cornerstones that should form basis for an ideal chemical process. This review analyzes accumulated experience achievements towards design products processes reduce or eliminate use generation hazardous substances. The presents views leading Russian scientists specializing various fields this subject, including homogeneous heterogeneous catalysis, fine basic organic synthesis, electrochemistry, polymer chemistry, based on bio-renewable feedstocks energetic compounds materials. A new approach to quantitative evaluation environmental friendliness by authors is described. <br> bibliography includes 1761.

Язык: Английский

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Regioselective Radical Alkylation of Arenes Using Evolved Photoenzymes

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(21), С. 11866 - 11874

Опубликована: Май 18, 2023

Substituted arenes are ubiquitous in molecules with medicinal functions, making their synthesis a critical consideration when designing synthetic routes. Regioselective C–H functionalization reactions attractive for preparing alkylated arenes; however, the selectivity of existing methods is modest and primarily governed by substrate's electronic properties. Here, we demonstrate biocatalyst-controlled method regioselective alkylation electron-rich electron-deficient heteroarenes. Starting from an unselective "ene"-reductase (ERED) (GluER-T36A), evolved variant that selectively alkylates C4 position indole, elusive using prior technologies. Mechanistic studies across evolutionary series indicate changes to protein active site alter character charge transfer (CT) complex responsible radical formation. This resulted significant degree ground-state CT complex. on C2-selective ERED suggest evolution GluER-T36A helps disfavor competing mechanistic pathway. Additional engineering campaigns were carried out C8-selective quinoline alkylation. study highlights opportunity use enzymes reactions, where small molecule catalysts struggle selectivity.

Язык: Английский

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