Molecular editing in natural product synthesis

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(5), С. 1451 - 1457

Опубликована: Янв. 1, 2022

Molecular editing entailing insertion and deletion of atom(s) enables new synthetic design the efficiency natural product synthesis could be improved.

Язык: Английский

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Photochemically Mediated Ring Expansion of Indoles and Pyrroles with Chlorodiazirines: Synthetic Methodology and Thermal Hazard Assessment

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(31)

Опубликована: Июнь 9, 2023

We demonstrate that arylchlorodiazirines serve as photo-activated halocarbene precursors for the selective one-carbon ring expansion of N-substituted pyrroles and indoles to corresponding pyridinium quinolinium salts. Preliminary investigations indicate same strategy also enables conversion pyrazoles pyrimidinium The N-substituent substrate plays an essential role in: (1) increasing scope by preventing product degradation, (2) enhancing yields suppressing co-product inhibition, (3) activating azinium products towards subsequent synthetic manipulations. This latter point is illustrated subjecting salts four complementary partial reductions, which provide concise access ring-expanded with different degrees increased C(sp

Язык: Английский

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Diversification of Indoles and Pyrroles by Molecular Editing: New Frontiers in Heterocycle‐to‐Heterocycle Transmutation

Chemistry - A European Journal, Год журнала: 2023, Номер 29(24)

Опубликована: Фев. 2, 2023

Skeletal editing via single-atom insertion reactions involving nitrogen heterocycles have been reported by two innovative and complementary methods for the conversion of pyrroles indoles to pyridines, quinolines quinazolines. The use electrophilic carbonyl cation equivalents in situ generated nitrenes enables molecular transform forming foundation best-selling pharmaceuticals. Considering importance medicinal chemistry, biology natural products, these offer approach complex structures heterocycle diversification peripheral editing.

Язык: Английский

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Rhodium-Catalyzed Intramolecular Nitrogen Atom Insertion into Arene Rings

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(32), С. 17570 - 17576

Опубликована: Авг. 3, 2023

In this study, we describe the direct insertion of an intramolecular nitrogen atom into aromatic C–C bond. transformation, carbamoyl azides are activated by a Rh catalyst and subsequently directly inserted bond arene ring to access fused azepine products. This transformation is challenging, owing existence competitive C–H amination pathway. The use paddlewheel dirhodium complex Rh2(esp)2 effectively inhibited undesired insertion. Density functional theory calculations were performed reveal reaction mechanism origin chemoselectivity Rh-catalyzed reactions. novel products highly robust allow for downstream diversification.

Язык: Английский

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Single-atom skeletal editing of 2H-indazoles enabled by difluorocarbene

Science China Chemistry, Год журнала: 2023, Номер 66(7), С. 1975 - 1981

Опубликована: Май 11, 2023

Язык: Английский

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