Bartłomiej Furman

The integration of sequential transformations requiring mutually incompatible conditions remains a fundamental challenge in synthetic chemistry. Here, we report a liquid‐assisted mechanochemical strategy that enables the one‐pot merging of base‐ and acid‐mediated processes within a single vessel, overcoming challenges associated with their integration under conventional solution‐phase conditions. This approach provides access to valuable N ‐heterocyclic scaffolds while reducing solvent use and improving overall process efficiency. The sequence is initiated by the mechanochemical copper‐catalyzed Ullmann–Goldberg CN coupling of unprotected β‐lactams with aryl iodides, which can be paused to afford N ‐aryl β‐lactams in up to 98% yield. A strategically implemented liquid‐assisted grinding (LAG) step enables seamless integration of the CN coupling step with an acid‐mediated Fries‐type rearrangement of amides, providing access to 2,3‐dihydroquinolin‐4‐ones in moderate to excellent yields under mechanochemical conditions. The protocol exhibits broad functional group tolerance, accommodates structurally complex substrates, and enables late‐stage functionalization. Gram‐scale mechanochemical synthesis of a key 2,3‐dihydroquinolin‐4‐one intermediate, followed by its direct conversion to the WHO‐listed antimalarial drug chloroquine under solvent‐free milling conditions, highlights the scalability and practical utility of this approach.

A novel and environmentally friendly method has been developed for the synthesis of a broad range of diarylamines from inexpensive and readily available starting materials, such as aromatic aldehydes and amines. The process follows a one-pot strategy in which imine formation is succeeded by an oxidative rearrangement analogous to the Meinwald reaction and concludes with a light-induced deformylation step. This efficient transformation proceeds in a single vessel with a high atom economy under mild, metal-free conditions. The methodology was further demonstrated as a key step in the synthesis of phentolamine, a reversible, nonselective α-adrenergic blocker used in the treatment of hypertensive emergencies.

A sustainable method for the synthesis of 2-deoxy lactones as direct precursors to 2-deoxy sugars via regioselective UV-light-driven dealkyloxylation of carbohydrate-derived lactones is detailed. This catalyst- and additive-free protocol utilizes light irradiation, providing high step economy and functional group compatibility. This environmentally friendly and straightforward approach enhances the synthetic toolbox for 2-deoxy sugars, which is vital in numerous biologically active molecules and drug candidates.

The development of straightforward synthetic methods for photoactive polycyclic aromatic hydrocarbons (PAHs) that avoid Pd‐catalyzed or radical‐based processes remains a challenge. Such methods are essential to reducing the cost and environmental impact of organic photodevices. In this work, we present a one‐pot synthetic approach for creating novel bipolar PAHs with extended π‐conjugation, which are not accessible via conventional Pd‐catalyzed routes. Our cascade process operates exclusively under basic conditions, utilizing cesium carbonate and molecular sieves to facilitate the coupling of electron‐deficient 4‐fluoronaphthalene‐1,8‐dicarboximide with halogenated electron‐rich moieties. This results in the regio‐ and chemoselective formation of new 6‐ and/or 5‐membered conjugated rings via consecutive SN_Ar reactions, as confirmed through experimental and computational studies. The resulting PAHs exhibit strong emissive properties, with quantum yields ranging from 34 % to 99 %. This work provides a simple and efficient synthetic strategy for producing novel semiconducting materials, offering a new framework for designing bipolar PAHs with distinct optical characteristics.

The development of straightforward synthetic methods for photoactive polycyclic aromatic hydrocarbons (PAHs) that avoid Pd‐catalyzed or radical‐based processes remains a challenge. Such methods are essential to reducing the cost and environmental impact of organic photodevices. In this work, we present a one‐pot synthetic approach for creating novel bipolar PAHs with extended π‐conjugation, which are not accessible via conventional Pd‐catalyzed routes. Our cascade process operates exclusively under basic conditions, utilizing cesium carbonate and molecular sieves to facilitate the coupling of electron‐deficient 4‐fluoronaphthalene‐1,8‐dicarboximide with halogenated electron‐rich moieties. This results in the regio‐ and chemoselective formation of new 6‐ and/or 5‐membered conjugated rings via consecutive SN_Ar reactions, as confirmed through experimental and computational studies. The resulting PAHs exhibit strong emissive properties, with quantum yields ranging from 34 % to 99 %. This work provides a simple and efficient synthetic strategy for producing novel semiconducting materials, offering a new framework for designing bipolar PAHs with distinct optical characteristics.

A comprehensive and sustainable protocol for the preparation of structurally diverse ortho - and para -cyclophanes via a light-promoted Fries-type intramolecular rearrangement of N -aryl lactams is presented.

Tertiary, morpholine-derived, fluoroalkyl amides have been found to be efficient, readily accessible, bench-stable surrogates of fluoroalkyl aldehydes. This discovery is applied to the one-pot synthesis of a symmetrical and, more challengingly, unsymmetrical meso-fluoroalkylated bis(heteroaryl)methanes via a Schwartz's reagent-mediated reductive activation. The usefulness of this approach for the introduction of a fluoromethylated carbon bridge was proven by implementation of the developed methodology in the synthesis of a fluorine-decorated bispyrromethane skeleton and an α-alkylated BODIPY core.

The photoexcited N-vinylazetidinones could undergo a ring expansion by a [1,3]-acyl shift to afford 2,3-dihydro-4-pyridones. A modular set-up was used for the studies in flow, with remote real-time control of the reaction course via UV-Vis.

An efficient approach for the synthesis of structurally diverse five-membered enaminones via a photo-Fries-type rearrangement of cyclic enamides in excellent yields is reported.