Carboxylic‐Phosphoric Anhydrides as Direct Electrophiles for Decarbonylative Hirao Cross‐Coupling of Carboxylic Acids: DFT Investigation of Mechanistic Pathway

Chemistry - An Asian Journal, Год журнала: 2023, Номер 18(7)

Опубликована: Фев. 7, 2023

In this anniversary issue, we present a DFT study of the mechanism decarbonylative Hirao cross-coupling carboxylic-phosphoric anhydrides to afford aryl phosphonates. Traditionally, direct activation carboxylic acids participate in couplings is performed presence acid anhydride activators. We discovered that dehydrogenative phosphorylation benzoic can be high yield via and coupling phosphite as dual activating nucleophilic reagent, enabling phosphorylation. Control studies demonstrated (acyl phosphate) an intermediate process. were conducted gain insight into process compare selectivity C-O P-O bond activations. Considering utility ubiquitous acids, alternative pathway may find applications for synthesis valuable molecules organic synthesis.

Язык: Английский

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Formation of C(sp2)–C(sp3) Bonds Instead of Amide C–N Bonds from Carboxylic Acid and Amine Substrate Pools by Decarbonylative Cross-Electrophile Coupling

Опубликована: Март 15, 2023

Carbonheteroatom bonds, most often amide and ester are the standard method to link together two complex fragments be-cause carboxylic acids, amines, alcohols ubiquitous reactions reliable. However, CN CO linkages a metabolic liability because they prone hydrolysis. While C(sp2)–C(sp3) preferable in many cases, methods make them require different starting materials or less functional-group compatible. We show here new, decarbonylative reaction that forms bonds from of activated acids (via 2-pyridyl esters) with alkyl groups derived amines N-alkyl pyridinium salts) halides). Key this process is remarkably fast, reversible oxidative addi-tion/decarbonylation sequence enabled by pyridone bipyridine ligands that, under conditions purge CO(g), lead selective reaction. The mild enough allow coupling more fragments, such as those used drug develop-ment, demonstrated typical Proteolysis Targeting Chimera (PROTAC) anchor common linkers via CC linkages.

Язык: Английский

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Catalyst Design and Feature Engineering to Improve Selectivity and Reactivity in Two Simultaneous Cross-Coupling Reactions

Journal of Chemical Information and Modeling, Год журнала: 2023, Номер 63(18), С. 5764 - 5772

Опубликована: Сен. 1, 2023

Highly active catalysts are required in numerous industrial fields; therefore, to minimize costs and development time, catalyst design using machine learning has attracted significant attention. This study focused on a reaction system where two types of cross-coupling reactions, namely, Buchwald-Hartwig type (BHCC) Suzuki-Miyaura (SMCC) occur simultaneously. Constructing machine-learning model that considers all experimental conditions is essential accurately predict the product yield for both BHCC SMCC reactions. The objective this was establish explanatory variables x considered within involving simultaneous cross-couplings achieve target novel To accomplish this, Bayesian optimization combined with established new enhance selectivity. Moreover, successfully pioneered reactions Cu, Rh, Pt did not previously react transition metals other than Ni or Pd.

Язык: Английский

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Unveiling Pre-Transmetalation Intermediates in Base-Free Suzuki–Miyaura Cross-Couplings: A Computational Study

Inorganic Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Янв. 24, 2024

The pre-transmetalation intermediates are critically important in Suzuki–Miyaura cross-coupling (SMC) reactions and have become a hot spot of the current research. However, under base-free conditions not been clear. Herein, comprehensive theoretical study is performed on Pd-catalyzed desulfonative SMC reaction. fragile coordination feature acceleration role RuPhos chelate ligand revealed. hydrogen-bond complex between Pd–F aryl boronic acid identified as an intermediate, which increases energy span to 32.5 kcal/mol. controlling factor for formation complexes attributed electronegativities halogen atoms metal halide complexes. What more, other reported reaction systems involving acids reconsidered suggest that widely exist stable with influencing catalytic activities. earth-abundant Ni-catalyzed further designed predicted higher activity than original

Язык: Английский

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DFT mechanistic study on the synthesis of 2-fluorinated allylic scaffolds via PdII-catalyzed defluorinative arylation of gem-difluorocyclopropanes with phenylboronic acids

Molecular Catalysis, Год журнала: 2024, Номер 562, С. 114194 - 114194

Опубликована: Май 8, 2024

Язык: Английский

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