A deconstruction-reconstruction strategy for pyrimidine diversification

Nature, Journal Year: 2024, Volume and Issue: 631(8019), P. 87 - 93

Published: May 2, 2024

Language: Английский

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Photocatalytic furan-to-pyrrole conversion

Science, 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

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Interrogation of Enantioselectivity in the Photomediated Ring Contractions of Saturated Heterocycles

Journal 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

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Tandem C/N-Difunctionalization of Nitroarenes: Reductive Amination and Annulation by a Ring Expansion/Contraction Sequence

Journal 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

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

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(7), P. 1975 - 1981

Published: May 11, 2023

Language: Английский

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Nitrogen atom insertion into arenols to access benzazepines

Chemical 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

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Synthesis of benzenes from pyridines via N to C switch

Chem, 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

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Visible photons as ideal reagents for the activation of coloured organic compounds

Chemical 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

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Synthesis of Collidine from Dinitrogen via a Tungsten Nitride

Journal 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

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N-Oxide-to-Carbon Transmutations of Azaarene N-Oxides

Organic 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

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