A Voltage-Controlled Strategy for Modular Shono-Type Amination

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(42), С. 28663 - 28668

Опубликована: Окт. 14, 2024

Shono-type oxidation to generate functionalized heterocycles is a powerful method for late-stage diversification of relevant pharmacophores; however, development beyond oxygen-based nucleophiles remains underdeveloped. The limited scope can often be ascribed constant current electrolysis resulting in potential drifts that oxidize desired nucleophilic partner. Herein, we report voltage-controlled strategy selectively broad substrates, enabling modular C-N bond formation from protected amine nucleophiles. We implement an electroanalytically guided workflow using cyclic voltammetry (CV) and differential pulse (DPV) identify potentials across range heterocyclic substrates. Controlled (CPE) generates α-functionalized products moderate good yields carbamate-, sulfonamide-, benzamide-derived importance voltage control further exemplified through systematic study comparing our developed CPE (CCE) protocols. Voltage-guided CCE traditionally optimized reveal the maintaining high selectivity over scope; case with morpholine-derived substrate illustrates negative impact drifting under CCE. Sulfonamide drugs, which have significant overlap model are rendered competent CPE. Lastly, sequential C-O functionalization difunctionalized pyrrolidines broadening utility this reaction.

Язык: Английский

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Biosynthesis, total synthesis, and biological profiles of Ergot alkaloids

˜The œAlkaloids. Chemistry and biology/˜The œalkaloids. Chemistry and biology, Год журнала: 2020, Номер unknown, С. 1 - 112

Опубликована: Сен. 30, 2020

Язык: Английский

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Discovery of Novel 3,4-Dichloroisothiazole-Containing Coumarins as Fungicidal Leads

Journal of Agricultural and Food Chemistry, Год журнала: 2021, Номер 69(14), С. 4253 - 4262

Опубликована: Апрель 1, 2021

Natural products are one of the resources for discovering novel fungicidal leads. As a natural fungicide, osthole was used as coumarin-based lead compound development fungicides. Here, series 3,4-dichloroisothiazole-containing 7-hydroxycoumarins were rationally designed, synthesized, and characterized by introducing bioactive substructure, 3,4-dichloroisothiazole, into coumarin skeleton. In vitro bioassay indicated that 7g displayed good activity against Rhizoctonia solani, Physalospora piricola, Sclerotinia sclerotiorum, Botrytis cinerea. Its median effective concentration (EC50) value each these fungi fell between 0.88 2.50 μg/mL, which much lower than corresponding pathogen (between 7.38 74.59 μg/mL). vivo screening validated 7k exhibited 100%, 60%, 20% efficacy R. solani Kühn at 200, 100, 50 respectively. RNA sequence analysis implied growth inhibition might result from potential disruptions fungal membrane formation intracellular metabolism. Furthermore, field experiment with cucumber plants 7b showed 62.73% 74.03% Pseudoperonospora cubensis (Berk. & Curt.) Rostov. rates 12.5 g a.i./ha 25 a.i./ha, respectively, no significant difference 30 a.i./ha. Our studies suggested 7b, 7g, be leads further optimization.

Язык: Английский

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Unified, Biosynthesis-Inspired, Completely Stereocontrolled Total Synthesis of All Highest-Order [n + 1] Oligocyclotryptamine Alkaloids

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(33), С. 23574 - 23581

Опубликована: Авг. 12, 2024

We describe the unified enantioselective total synthesis of polycyclotryptamine natural products (+)-quadrigemine H, (+)-isopsychotridine C, (+)-oleoidine, and (+)-caledonine. Inspired by our hypothesis for biogenesis these alkaloids via an iterative concatenative addition homochiral cyclotryptamines to a

Язык: Английский

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Mitsunobu reaction: assembling C–N bonds in chiral traditional Chinese medicine

RSC Advances, Год журнала: 2025, Номер 15(7), С. 5167 - 5189

Опубликована: Янв. 1, 2025

The Mitsunobu reaction is a key bimolecular nucleophilic substitution for synthesizing chiral products. This paper highlights its importance in biologically active compounds, focusing on forming C–N single bonds.

Язык: Английский

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