Taming nonclassical carbocations to control small ring reactivity

Science Advances, Год журнала: 2024, Номер 10(2)

Опубликована: Янв. 12, 2024

Prediction of the outcome ring opening small organic rings under cationic conditions can be challenging due to intermediacy nonclassical carbocations. For example, solvolysis cyclobutyl or cyclopropylmethyl derivatives generates up four products on nucleophilic capture elimination via cyclopropylcarbinyl and bicyclobutonium ions. Here, we show that such reaction outcomes controlled by subtle changes structure carbocation. Using bicyclo[1.1.0]butanes as cation precursors, regio- stereochemistry is shown depend degree nature substituents intermediates. Reaction are rationalized using computational models, resulting in a flowchart predict product formation from given precursor.

Язык: Английский

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Precision single-atom editing: new frontiers in nitrogen insertion and substitution for the generation of N-heterocycles

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(14), С. 4041 - 4053

Опубликована: Янв. 1, 2024

This paper primarily focuses on the editing of nitrogen atoms, encompassing insertion N, substitution C with and utilization 15 N in place 14 for construction N-heterocycles.

Язык: Английский

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Stereospecific molecular rearrangement via nucleophilic substitution at quaternary stereocentres in acyclic systems

Nature Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Март 19, 2025

Язык: Английский

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Bioinspired intramolecular spirocyclopropanation of quinones as an interrupted photoredox process

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(20), С. 5703 - 5711

Опубликована: Янв. 1, 2024

Small molecules, such as trimethylamine N -oxide, interrupt intramolecular photoreactions of quinones by proton transfer and allow to convert a variety spirocyclopropanes in catalytic, diastereoselective, atom-conserving manner.

Язык: Английский

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Biomimetic Synthesis of Azorellolide via Cyclopropylcarbinyl Cation Chemistry

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Дек. 18, 2024

A concise synthesis of the complex diterpene azorellolide, inspired by speculations on biosynthetic cationic cascades, is presented. The approach, guided computation, relies intramolecular interception a cyclopropylcarbinyl cation an appended carboxylate. successful execution this strategy was achieved through acid-catalyzed isomerization β-lactone in competition with type I dyotropic rearrangement.

Язык: Английский

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Visible-Light-Photocatalyzed Self-Cyclopropanation Reactions of Dibenzoylmethanes for the Synthesis of Cyclopropanes

Organic Letters, Год журнала: 2024, Номер 26(27), С. 5752 - 5757

Опубликована: Июль 1, 2024

A new self-cyclopropanation of 1,3-diphenylpropane-1,3-dione, leading to tetrasubstituted cyclopropane containing three contiguous stereogenic centers with high stereoselectivity, has been achieved through violet-light-emitting diode-irradiated photocatalysis, featuring both cycloaddition and a distinctive rearrangement. Diverging from conventional cyclopropanation pathways, this reaction yields unprecedented rearrangement cascade reactions.

Язык: Английский

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Photoredox-Catalyzed Regioselective 1,3-Alkoxypyridylation of gem-Difluorocyclopropanes

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Дек. 4, 2024

Difluoromethylene and pyridine cores are very important structural units in medicinal chemistry. Herein, we report the development of photoredox-catalyzed ring-opening 1,3-alkoxypyridylation gem-difluorinated cyclopropanes using 4-cyanopyrines alcohols, employing cyclopropane radical cations as key intermediate. The reaction exhibits high regioselectivity under mild conditions can also be practiced on gram-scale synthesis, telescoped reaction, late-stage functionalization biological molecules.

Язык: Английский

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Halogen Promoted Desulfurative Cleavage of Cyclopropylmethyl Thioethers and Amination of the Formed Cyclopropylcarbinyl Cations

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(20)

Опубликована: Март 20, 2024

Abstract Cyclopropylmethyl sulfides react with N ‐fluorosulfonimide (NFSI) or molecular iodine, enabling C−S cleavage to generate cyclopropylcarbinyl cations, which evolve through cyclopropane ring‐opening reactions into homoallyl cations suitable nucleophiles present in the reaction media. This desulfurative of cyclopropylmethyl thioethers under non‐acidic conditions facilitates homoallylation ‐based such as alkyl aryl amines well sulfonimides a one‐pot protocol one two steps depending on nucleophile. The is initiated by halogen‐sulfur bond that causes cleavage. Moreover, iodine proceeds iodide intermediates.

Язык: Английский

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Strategic convergent synthesis en route to Veratrum steroidal alkaloids

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(14), С. 4014 - 4023

Опубликована: Янв. 1, 2024

In this Highlight, the convergent synthetic approaches that yield highly functionalized, complex molecular architecture of Veratrum steroidal alkaloids are discussed.

Язык: Английский

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Asymmetric Synthesis of Bis-spiro Cyclopropane Skeletons via Bifunctional Phosphonium Salt-catalyzed [2 + 1] Annulation

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(23), С. 6666 - 6671

Опубликована: Янв. 1, 2024

A new approach for constructing enantiopure spiroskeletons was developed via bifunctional phosphonium salt-catalyzed [2 + 1] annulation. These novel scaffolds have potential to facilitate the discovery and development of chiral drugs.

Язык: Английский

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