Diastereoselective Synthesis of Aryl C‐Glycosides from Glycosyl Esters via C−O Bond Homolysis

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(17), P. 9433 - 9438

Published: Jan. 15, 2021

C-aryl glycosyl compounds offer better in vivo stability relative to O- and N-glycoside analogues. glycosides are extensively investigated as drug candidates applied chemical biology studies. Previously, were derived from lactones, glycals, stannanes, halides, via methods displaying various limitations with respect the scope, functional-group compatibility, practicality. Challenges remain synthesis of nucleosides 2-deoxysugars easily accessible carbohydrate precursors. Herein, we report a cross-coupling method prepare heteroaryl glycosides, including 2-deoxysugars, esters bromoarenes. Activation substrates leverages dihydropyridine (DHP) an activating group followed by decarboxylation generate radical C-O bond homolysis. This strategy represents new means activate alcohols partner. The convenient preparation their exemplifies potential this medicinal chemistry.

Language: Английский

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Deaminative Reductive Cross-Electrophile Couplings of Alkylpyridinium Salts and Aryl Bromides

Organic Letters, Journal Year: 2019, Volume and Issue: 21(8), P. 2941 - 2946

Published: March 27, 2019

A nickel-catalyzed reductive cross-coupling of alkylpyridinium salts and aryl bromides has been developed using Mn as the reductant. Both primary secondary can be used, high functional group heterocycle tolerance is observed, including for protic groups. Mechanistic studies indicate formation an alkyl radical, controlling its fate was key to success this reaction.

Language: Английский

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Dialkylation of 1,3-Dienes by Dual Photoredox and Chromium Catalysis

ACS Catalysis, Journal Year: 2019, Volume and Issue: 10(2), P. 1621 - 1627

Published: Dec. 18, 2019

The direct conversion of feedstock chemicals into value-added products is broad interest in chemical research. Herein, we present a regioselective and diastereoselective three-component dialkylation 1,3-dienes with Hantzsch esters aldehydes for the synthesis homoallylic alcohols. reaction enabled by dual photoredox chromium catalysis can also be performed enantioselectively employing chromium-bisoxazoline complexes.

Language: Английский

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Using Data Science To Guide Aryl Bromide Substrate Scope Analysis in a Ni/Photoredox-Catalyzed Cross-Coupling with Acetals as Alcohol-Derived Radical Sources

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(2), P. 1045 - 1055

Published: Jan. 5, 2022

Ni/photoredox catalysis has emerged as a powerful platform for C(sp2)–C(sp3) bond formation. While many of these methods typically employ aryl bromides the C(sp2) coupling partner, variety aliphatic radical sources have been investigated. In principle, reactions enable access to same product scaffolds, but it can be hard discern which method because nonstandardized sets are used in scope evaluation. Herein, we report Ni/photoredox-catalyzed (deutero)methylation and alkylation halides where benzaldehyde di(alkyl) acetals serve alcohol-derived sources. Reaction development, mechanistic studies, late-stage derivatization biologically relevant chloride, fenofibrate, presented. Then, describe integration data science techniques, including DFT featurization, dimensionality reduction, hierarchical clustering, delineate diverse succinct collection that is representative chemical space substrate class. By superimposing examples from published on this space, identify areas sparse coverage high versus low average yields, enabling comparisons between prior art new method. Additionally, demonstrate systematically selected quantify population-wide reactivity trends reveal possible functional group incompatibility with supervised machine learning.

Language: Английский

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Metal-catalysed C–Het (F, O, S, N) and C–C bond arylation

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(16), P. 8903 - 8953

Published: Jan. 1, 2021

The formation of C–aryl bonds has been the focus intensive research over last decades for construction complex molecules from simple, readily available feedstocks.

Language: Английский

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