Recent advances in the synthesis of trifluoromethyl-containing heterocyclic compounds via trifluoromethyl building blocks

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(31), С. 6246 - 6276

Опубликована: Янв. 1, 2024

Recent advances in the preparation of trifluoromethyl-containing heterocyclics via trifluoromethyl building block strategies over period from 2019 to present are systematically summarized and discussed.

Язык: Английский

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Generation of Stereocenters via Single-Carbon-Atom Doping Using N-Isocyanides

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Фев. 28, 2025

Atomic carbon remains a challenging species for organic synthesis despite its potential to form four covalent bonds in single step. Single-carbon-atom doping (SCAD) offers powerful approach enhancing molecular complexity one process without atom loss. However, synthetically viable SCAD reactions capable of generating stereocenters have not been realized. Here, we report an reaction that creates by unlocking the reactivity (N-isocyanoimino)phosphorane as atomic equivalent. This reagent facilitates single-step conversion various acyl chlorides into homologated α-chloro cyclic ketones, proceeding via formation different bonds: C-Cl, C-H, and two C-C at incorporated atom.

Язык: Английский

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Asymmetric multi-component trifunctionalization reactions with α-Halo Rh-carbenes

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Фев. 7, 2025

Multi-component multi-functionalization reactions involving active intermediates are powerful tools for rapidly generating a wide array of compounds. Metal carbynoids, with their distinct reactivity, hold great promise developing synthetic methodologies. However, application in catalytic transfer has been hindered by the limited availability suitable precursors. In this study, we investigate potential α-halo Rh-carbenes, leveraging concept metal carbynoids reactions. Through chiral phosphoric acid-catalyzed asymmetric trifunctionalization, have developed method synthesizing variety α-cyclic ketal β-amino esters high yields and excellent enantioselectivity. Our extensive experimental computational studies reveal that Rh-carbenes exhibit carbynoid properties, which facilitate transformation into functionalized Fischer-type through decomposition C-halo bond.

Язык: Английский

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Recent progress in the synthesis of imidazoquinoline derivatives

Results in Chemistry, Год журнала: 2025, Номер unknown, С. 102270 - 102270

Опубликована: Апрель 1, 2025

Язык: Английский

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Photoinduced [3 + 2] Radical Cyclization of α-Diazodifluoroethyl Sulfonium Salt with Hydrazones

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Май 12, 2025

Here we report a photoinduced [3 + 2] radical cyclization reaction of α-diazodifluoroethane sulfonium reagent with hydrazones to give the corresponding N-amino-4-difluoromethyl-1,2,3-triazoles. This transformation proceeds under simple blue light irradiation conditions without need photocatalyst. Preliminary mechanistic studies indicate that formation an electron donor-acceptor (EDA) complex between electron-deficient α-diazo triflate and electron-rich hydrazone operates as key mediator.

Язык: Английский

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Stereodivergent Four-Component Reactions via Rh-Carbynoids

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Май 27, 2025

Multicomponent reactions (MCRs) provide a robust platform for the modular assembly of structurally complex molecules, while higher-order MCRs (≥4 components) exponentially expand accessible chemical space. Although Rh-carbynoids exhibit significant potential developing due to their unique reactivity, application in asymmetric four-component (4CRs) has been hindered by competing nucleophilic reactivities and stereochemical control. Herein, we overcome these challenges integrating N- C-nucleophiles report an 4CR involving hypervalent iodine diazo reagents, carbamates, N,N-dialkylanilines, imines. This strategy represents first utilizing Rh-carbynoids, achieving sequential formation C(sp3)-N, C(sp3)-C(sp2), C(sp3)-C(sp3) bonds at single carbon center. The method provides stereodivergent access α,β-diamino-3-arylpropanoic acid derivatives bearing two contiguous stereocenters with good yields exceptional enantioselectivity.

Язык: Английский

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Photoredox-Catalyzed [2 + 1 + 2] Cyclization of Alkenes, Carbyne Equivalents, and Nitriles

ACS Catalysis, Год журнала: 2025, Номер unknown

Опубликована: Май 30, 2025

Язык: Английский

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Multi-functionalization of Rh-carbynoids with alcohols/carbamates and α-propargylic-3-indolymethanols

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(13), С. 3596 - 3601

Опубликована: Янв. 1, 2024

This work represents the first example of interception a di-heteroatom ylide through an S N 1-type process, enabling multicomponent trifunctionalization Rh-carbynoids.

Язык: Английский

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Regioselective Synthesis of Multisubstituted Fluoropyrazoles via Silver‐Catalyzed One‐Pot Cyclization Reaction of Diazo Reagents with Fluoronitroalkenes

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(16), С. 3516 - 3521

Опубликована: Май 8, 2024

Abstract A silver‐catalyzed regioselective one‐pot cyclization reaction of diazo reagents with fluoronitroalkenes was developed. This transformation presents a method for accessing series 4‐aryl‐3‐fluoropyrazoles that are substituted various groups such as trifluoromethyl, carboxylic ester, nitrile, and phosphonate ester. Further synthetic transformations offered the corresponding fluorinated trifluoromethylated analogues two fungicide compounds.

Язык: Английский

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Generation of Stereocenters via Single-Carbon-Atom Doping Using N-Isocyanides

Опубликована: Авг. 7, 2024

Among the electronically unsaturated carbon species, atomic is most challenging to use for synthesis of organic molecules, despite its potential forge four distinct covalent bonds at a center in single process. Single-carbon-atom doping (SCAD) into molecules without loss atoms reactant highly attractive because it allows remarkable increase molecular complexity We have previously reported that N-heterocyclic carbenes can serve as an equivalent suitable SCAD reactions. However, method limited formation methylene carbons, leaving full concept unrealized. Here, we report reaction results stereocenters by unlocking reactivity (N-isocyanoimino)triphenylphosphorane equivalent. This reagent enables single-step conversion range acyl chlorides homologated α-chloro cyclic ketones, which proceeds via generation different bonds, i.e., one C-Cl, C-H, and two C-C incorporated atom.

Язык: Английский

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