A machine-learning tool to predict substrate-adaptive conditions for Pd-catalyzed C–N couplings

Science, Год журнала: 2023, Номер 381(6661), С. 965 - 972

Опубликована: Авг. 31, 2023

Machine-learning methods have great potential to accelerate the identification of reaction conditions for chemical transformations. A tool that gives substrate-adaptive palladium (Pd)-catalyzed carbon-nitrogen (C-N) couplings is presented. The design and construction this required generation an experimental dataset explores a diverse network reactant pairings across set conditions. large scope C-N was actively learned by neural models using systematic process experiments. showed good performance in validation: Ten products were isolated more than 85% yield from range with out-of-sample reactants designed challenge models. Importantly, developed workflow continually improves prediction capability as corpus data grows.

Язык: Английский

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Nickel-Catalyzed Hydrofluorination in Unactivated Alkenes: Regio- and Enantioselective C–F Bond Formation

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(13), С. 9375 - 9384

Опубликована: Март 21, 2024

Catalytic formation of a regio- and enantioselective C–F bond chiral center from readily available alkenes is crucial goal, yet it continues to pose significant challenges in organic synthesis. Here, we report the regioselective bonds facilitated by NiH catalysis coordination directing strategy that enables precise hydrofluorination both terminal internal alkenes. Notably, have optimized this methodology achieve high enantioselectivity creating aliphatic stereogenic centers especially with β,γ-alkenyl substrates, using tailored Bn-BOx ligand. Another pivotal finding our research identification (+)-nonlinear effect under conditions, allowing for even moderately enantiomerically enriched ligands. Given role fluorine pharmaceuticals synthetic materials, offers essential insights into centers, paving way efficient production valuable fluorinated compounds.

Язык: Английский

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Visible-Light-Driven Synergistic Se/Fe Catalysis for the Synthesis of 2-Aminoquinoline Derivatives

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 3, 2025

A visible-light-driven Se/Fe synergistic catalytic reaction between isocyanides and amines has been developed, employing air as the terminal oxidant. This efficient strategy offers facile access to 2-aminoquinoline scaffolds. The use of cost-effective readily available Fe(OTf)3 modulates selenium catalyst's oxidation state, enhancing method's environmental friendliness practicality. protocol is further distinguished by its good yields, broad substrate scope, mild conditions.

Язык: Английский

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Modular synthesis of fluorinated 2H-thiophenes via [4 + 1] cyclization of enaminothiones

Organic & Biomolecular Chemistry, Год журнала: 2023, Номер 21(16), С. 3345 - 3349

Опубликована: Янв. 1, 2023

An efficient and straightforward synthetic method for constructing trifluoromethyl 2H-thiophenes through [4 + 1] cycloaddition of enaminothiones with N-tosylhydrazones has been disclosed. The platforms were found to be compatible a broad substrate scope show high regio- stereo-selectivities under very mild reaction conditions such as room temperature, neutral media low loading catalyst.

Язык: Английский

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Rapid (Deuterio)difluoromethylation of Heteroatoms Using R‐22 Gas: A Demonstration of Flow Chemistry in Suppressing Intrinsic Reaction Pathways

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(21), С. 4385 - 4391

Опубликована: Июль 23, 2024

Abstract R‐22 gas (ClCF 2 H) is utilized in continuous flow for the installation of CF H and D groups on heteroatoms. A judiciously designed system suppresses intrinsic S N reaction between heteroatom anions ClCF H, allowing selective carbene‐based fragment coupling to yield X‐CF products with deuterium incorporation levels up 96%. broad scope X–CF (X=S, O, N) obtained a short residence time 5 minutes scalability demonstrated.

Язык: Английский

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Nickel-Catalyzed Regio- and Enantioselective Hydrofluorination in Unactivated Alkenes

Synlett, Год журнала: 2024, Номер 36(02), С. 97 - 102

Опубликована: Май 28, 2024

Abstract While enantioselective hydrofluorination methods for activated alkenes represent a notable advance, the resultant enantiomeric excesses remain largely moderate, indicating necessity enhancements in precision, efficiency, and scope. We have recently developed an innovative nickel hydride catalytic system that enables regio- C–F bond formation with unactivated alkenes. By utilizing specially designed Bn-BOx ligands improved selectivity, our approach demonstrates exceptional efficiency selectivity β,γ-alkenyl amide substrates. This breakthrough enhances synthesis of organofluorine compounds, marking significant advancement organic synthesis. 1 Introduction 2 Reaction Design Hydrofluorination 3 Regio- Enantioselective 4 Asymmetric Amplification 5 Conclusions

Язык: Английский

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The Difluoromethylation Protocols

Patai's chemistry of functional groups, Год журнала: 2024, Номер unknown, С. 1 - 75

Опубликована: Дек. 23, 2024

Abstract Difluoromethyl compounds have found increasingly important applications in the fields of pharmaceuticals and agrochemicals due to unique biological properties CF 2 H group. The past decade has witnessed development an impressive array new reagents strategies for efficient difluoromethylation. This review aims summarize state‐of‐the‐art advances difluoromethylation according following four categories: electrophilic difluoromethylation, nucleophilic radical transition‐metal mediated

Язык: Английский

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Introducing Bis(5-(Trifluoromethyl)pyridin-2-yl)amine Chelating Unit via Pd-Catalyzed Amination

Molbank, Год журнала: 2024, Номер 2024(2), С. M1831 - M1831

Опубликована: Июнь 4, 2024

We report a one-step synthesis of trifluoromethyl-substituted di(pyridin-2-yl)amine-based ligands. N-(hetero)aryl-substituted bis(5-(trifluoromethyl)pyridin-2-yl)amines were obtained from 2-bromo-5-(trifluoromethyl)pyridine and corresponding aromatic amines via Pd-catalyzed amination reaction in the presence Pd(dba)2/BINAP catalytic system. Four new ligands prepared good to high yields characterized by NMR, IR spectroscopies mass spectrometry. The structure one products was additionally supported X-ray analysis.

Язык: Английский

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Synthesis of α,α-Difluoromethylene Amines from Thioamides Using Silver Fluoride

The Journal of Organic Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Сен. 18, 2024

We developed a mild, rapid process employing AgF and thioamides to produce α,α-difluoromethylene amines efficiently. This method exhibited remarkable tolerance toward various functional groups present in

Язык: Английский

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