
Nature Synthesis, Journal Year: 2025, Volume and Issue: unknown
Published: March 7, 2025
Language: Английский
Nature Synthesis, Journal Year: 2025, Volume and Issue: unknown
Published: March 7, 2025
Language: Английский
Nature, Journal Year: 2024, Volume and Issue: 631(8019), P. 87 - 93
Published: May 2, 2024
Language: Английский
Citations
20Science, Journal Year: 2024, Volume and Issue: 386(6717), P. 99 - 105
Published: Oct. 3, 2024
The identity of a heteroatom within an aromatic ring influences the chemical properties that heterocyclic compound. Systematically evaluating effect single atom, however, poses synthetic challenges, primarily as result thermodynamic mismatches in atomic exchange processes. We present photocatalytic strategy swaps oxygen atom furan with nitrogen group, directly converting into pyrrole analog intermolecular reaction. High compatibility was observed various derivatives and nucleophiles commonly used drug discovery, late-stage functionalization furnished otherwise difficult-to-access pyrroles from naturally occurring furans high molecular complexity. Mechanistic analysis suggested polarity inversion through electron transfer initiates redox-neutral processes at room temperature.
Language: Английский
Citations
19Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 2, 2025
We recently reported a chiral phosphoric acid (CPA) catalyzed enantioselective photomediated ring contraction of piperidines and other saturated heterocycles. By extruding single heteroatom from ring, this transformation builds desirable C(sp3)–C(sp3) bonds in the contracted products; however, origins enantioselectivity remain poorly understood. In work, has been explored across an expanded structurally diverse substrate scope, revealing wide range enantioselectivities (0–99%) using two distinct CPA catalysts. Mechanistic investigations support rate-determining excitation that generates short-lived achiral intermediates are intercepted by enantiodetermining closure. The effects competitive uncatalyzed reactivity light-driven reversibility closure on have elucidated. Statistical models were built regressing scope against key structural features products for both resultant suggested factors influence response each catalyst enabled rational modification pharmaceutically relevant target molecule to improve enantioselectivity. Finally, density functional theory (DFT)-based transition state analysis identified noncovalent interactions with correlated unique selectivity-relevant uncovered through statistical modeling. Our findings not only offer comprehensive insight into system but should also aid future development related CPA-catalyzed reactions.
Language: Английский
Citations
4Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 145(1), P. 41 - 46
Published: Dec. 23, 2022
A synthetic method for the reductive transformation of nitroarenes into ortho-aminated and -annulated products is reported. The operates via exhaustive deoxygenation by an organophosphorus catalyst a mild terminal reductant to access aryl nitrenes, which after ring expansion, are trapped amine nucleophiles give dearomatized 2-amino-3H-azepines. Treatment these ring-expanded intermediates with acyl electrophiles triggers 6π electrocyclization extrude nitrogen atom restore aromaticity phenyl ring, delivers C–H functionalization 2-aminoanilide benzimidazole products.
Language: Английский
Citations
47Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(7), P. 1975 - 1981
Published: May 11, 2023
Language: Английский
Citations
29Chemical Science, Journal Year: 2024, Volume and Issue: 15(7), P. 2612 - 2617
Published: Jan. 1, 2024
Advances in site-selective molecular editing have enabled structural modification on complex molecules.
Language: Английский
Citations
16Chem, Journal Year: 2024, Volume and Issue: 10(6), P. 1940 - 1949
Published: June 1, 2024
The skeletal editing of heteroarenes introduces new disconnections to the chemistry lexicon, enabling interconversion ring systems via selective breaking/re-making carbon framework. We describe one-pot transformation pyridines into benzene derivatives, using a nucleophilic addition ring-opening/ring-closing (ANRORC) process with soft nucleophiles such as malonate. Triflic anhydride activates pyridine ANRORC synthesis an isolable amine intermediate, which aromatizes on simple heating. reaction has been exemplified room temperature protocol, along direct syntheses drug-like, tertiary-alkylated, and isotopically labeled benzoates.
Language: Английский
Citations
14Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(10), P. 4926 - 4975
Published: Jan. 1, 2024
In search for the perfect wave(length). This review is dedicated to recent efforts in development of visible light driven photochemical strategies occurring coloured organic compounds.
Language: Английский
Citations
13Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(12), P. 7979 - 7984
Published: March 15, 2024
The synthesis of pyridines from dinitrogen in homogeneous solution is known to be challenging considering that an N2 cleavage step needs combined with two N–C coupling steps. Herein, a tungsten complex bearing tailor-made 2,2′-(tBu2As)2-substituted tolane ligand scaffold was shown split afford the corresponding nitride, which not case for (iPr2As)2-substituted derivative. former nitride then reacted 2,4,6-trimethylpyrylium triflate, led formation oxo complex, along collidine. Over course this reaction, O atom pyrylium starting material replaced N via hitherto unprecedented skeletal editing process.
Language: Английский
Citations
12Organic Letters, Journal Year: 2024, Volume and Issue: 26(20), P. 4280 - 4285
Published: May 13, 2024
Reactions that change the identity of an atom within a ring system are emerging as valuable tools for site-selective editing molecular structures. Herein, we describe expansion underdeveloped transformation directly converts azaarene-derived N-oxides to all-carbon arenes. This transmutation exhibits good functional group tolerance and replaces N-oxide moiety with either unsubstituted, substituted, or isotopically labeled carbon atoms in single laboratory operation.
Language: Английский
Citations
11