Enrico

Self-powered wearable biosensor for continuous sweat lactate monitoring.

The continuous monitoring of sweat lactate is a critical task in sports and medical applications. This paper introduces a self-powered biosensor for the continuous monitoring of sweat lactate. A biofuel cell (BFC)is prepared using thionine as a bioanode mediator, with poly(ethylene glycol) diglycidyl ether and a chitosan–genipin membrane incorporated in the bioanode. This system achieves an open-circuit voltage of 0.75 V and output power density of 0.163 mW cm^–2 in the presence of 100 mM lactate. The self-powered biosensor is constructed by integrating the BFC with a voltage booster and Bluetooth transmitter. An on-body test is conducted on an exercising individual. The output signal of the self-powered biosensor is converted into lactate concentrations through manual pH adjustment. A correlation between the lactate concentrations in sweat and blood is observed. Overall, the proposed self-powered lactate biosensor can continuously monitor sweat lactate, with potential applications in the sports and medical domains.

We report a safe and scalable flow-based strategy for the on-demand generation of NCF₂R anions using a packed-bed microreactor containing CsF. This protocol enables the late-stage installation of the CF₂ group under mild conditions leveraging three points of diversification, allowing efficient access to a broad range of NCF₂R scaffolds.

Abstract

The α,α-difluoromethylene amine (NCF₂R) motif represents a useful functionality in medicinal chemistry, yet practical and modular methods to access this class of compounds are lacking. Here, we report a safe and scalable flow-based strategy for the on-demand generation of NCF₂R anions using a packed-bed microreactor containing caesium fluoride. This protocol enables the late-stage installation of the CF₂ group under mild conditions, avoiding the use of hazardous fluorinating agents and minimizing fluorinated waste. This fully modular strategy features three points of diversification (carboxylic acid, sulfonamide, and electrophile), allowing efficient access to a broad range of α,α-difluoromethylene amines. The method tolerates a variety of functional groups, supports late-stage functionalization of pharmaceutically relevant scaffolds, and is compatible with downstream cross-coupling reactions, demonstrating the robustness of the reaction protocol. This work provides a versatile platform for the streamlined incorporation of NCF₂ motifs, expanding the range of synthetic strategies available in medicinal and fluorine chemistry.

The first and asymmetric total synthesis of clerodin is reported. Key transformations included titanium(III) catalyzed cyclization of an epoxide ene-yne compound containing an internal oxygenated methyl-bearing alkene, metallaphotoredox-enabled deoxygenative coupling of an alcohol, and SmI₂-mediated elimination of a pre-installed acetal to establish the 2,3-dihydrofuran motif.

Abstract

The first and asymmetric total synthesis of clerodin, the earliest isolated clerodane diterpenoid, has been achieved by tail-to-head cyclization and modular synthetic strategies. The C19 oxidized trans-decalin core was constructed via a tail-to-head cyclization of an epoxide ene-yne compound containing an internal oxygenated methyl-bearing alkene. This process involved a titanium(III) catalyzed epoxide ring-opening/ene-yne cyclization. The furan fragment was assembled through a metallaphotoredox-enabled deoxygenative coupling of an alcohol precursor. A SmI₂-mediated elimination of a pre-installed acetal established the 2,3-dihydrofuran motif.

A mild, scalable electrocatalytic method for direct lactonization of benzylic alcohols to phthalides using N-hydroxyphthalimide as a redox mediator is reported. This metal-free process proceeds via a phthalimide-N-oxyl-mediated hydrogen atom transfer mechanism, shows broad scope with good to excellent yields, and enables late-stage functionalizations, including syntheses of talopram and a Y5 receptor antagonist intermediate.

A sustainable and efficient electrochemical method for the direct oxidative lactonization of benzylic alcohols, enabling rapid access to isobenzofuran-1(3H)-ones (phthalides) is presented. This electrocatalytic transformation leverages N-hydroxyphthalimide as a redox mediator under mild, metal-free conditions, offering an environmentally friendly alternative to traditional oxidation protocols. The method demonstrates broad substrate scope and delivers phthalide derivatives consistently in good to excellent yields. Mechanistic studies, combining cyclic voltammetry and density functional theory calculations, support a radical-mediated hydrogen atom transfer mechanism driven by phthalimide-N-oxyl radicals. Importantly, the utility of the protocol extends beyond model substrates: it is successfully applied to the synthesis of pharmaceutically relevant compounds, including talopram and a key intermediate for a neuropeptide Y5 receptor antagonist. Overall, this work underscores the power of electrosynthesis in modern organic chemistry, merging green chemistry principles with synthetic efficiency.

The efficient electrochemical synthesis of aromatic nitriles, important base chemicals in the chemical industry, is reported. Starting from toluene or analogues, the corresponding nitriles are produced in a one-pot two-step protocol with readily available chemicals and materials. This is a sustainable, ecofriendly and atom efficient alternative in comparison to existing synthetic methods.

Aromatic nitriles are extensively produced chemicals with a wide variety of applications. The high demand of these compounds justifies the search for sustainable synthesis alternatives using renewable energy. Here, an electrochemical oxidation of toluene and xylene derivatives to aromatic nitriles using NH₃ and H₂O under ambient conditions in a one-pot, two-step protocol is reported. In a first step, the toluene derivative is oxidized in the absence of a catalyst to the aldehyde. In the second step, ammonia is added together with LiI as an electrocatalyst to obtain the nitrile. The reaction network and mechanism are investigated using control experiments and cyclic voltammetry.

Chemodivergent Higher-Order Annulation of Azaheptafulvenes with Enals through N-Heterocyclic Carbene Catalysis.

A base-directed, chemodivergent, higher-order annulation between azaheptafulvenes and enals has been developed through N-heterocyclic carbene catalysis. In the presence of an N-heterocyclic carbene organocatalyst, DBU promotes an [8 + 3] annulation with excellent chemo- and diastereoselectivities, whereas the reaction proceeds via an [8 + 2] annulation when potassium carbonate is used as the base. In addition, the reaction can be carried out on a gram scale, and the products are efficiently converted into bicyclic derivatives.

A nickel catalyzed electrochemical cross-electrophile coupling approach for the base-free synthesis of (un)symmetric (hetero)aryl and alkyl sulfides from organic halides and disulfides is described. The reaction is broadly applicable and tolerates water and air atmosphere.

A formal cross-electrophile coupling approach enables the base-free synthesis of (un)symmetric (hetero)aryl and alkyl sulfides from organic halides and disulfides. This water and air-tolerant process utilizes the addition of electrochemically generated thiolate to an in situ-generated reactive nickel species.

Nature, Published online: 17 September 2025; doi:10.1038/d41586-025-02930-y

Electrochemical dehydration reactions are a fascinating and underexplored field of research in the domain of electrosynthesis. They offer a sustainable alternative to hazardous and harsh dehydration reagents. In this review, the recent progress that has been made in this emerging research topic is surveyed.

Electrochemical dehydration reaction is a fascinating and underexplored field of research, which has started to attract significant attention in recent years. Dehydration reactions are characterized by the formal removal of water in the course of the transformation, and they are among the most fundamental types of reactions found throughout chemistry. Examples are esterification reactions, amidation reactions, and the synthesis of carbon-heteroatom multiple bonds. In general, dehydration reactions are not considered to be redox reactions, because no oxidation states change in the substrate from which water is eliminated or in the dehydration reagent that is utilized. At first glance, there does not seem to be a link between dehydration reactions and redox chemistry. In recent years, however, it has been demonstrated that dehydration reactions can be carried out by electrolysis. Given the enormous importance of dehydration reactions from academic to technical scale, electrochemical dehydration reactions offer a more sustainable approach to such transformations. In this review, the recent progress is surveyed and the opportunities of this new and evolving field are highlighted. Electrochemical dehydration reactions are an interesting new discipline in the emerging domain of electroorganic chemistry, which is currently experiencing a remarkable renaissance to establish itself as a 21st-century technique.

Nature Chemistry, Published online: 02 September 2025; doi:10.1038/s41557-025-01904-x

The first organocatalytic enantioselective [4 + 4] cycloaddition of furan ortho-quinodimethanes is presented. The reaction proceeds in good yields and with high enantioselectivities allowing for the formation of novel classes of cyclooctanoids. DFT calculations point to an intriguing mechanism, where the stereochemical outcome is attributed to protonation of the catalyst-bound intermediate in the stereo-determining step.

Abstract

The enantioselective [4 + 4] cycloaddition for the construction of cyclooctanoids is a challenging transformation in organic chemistry. Herein, we present the first organocatalytic enantioselective [4 + 4] cycloaddition of furan ortho-quinodimethanes, activated by dearomatization of the heteroaromatic compound, which thereby allows for the cycloaddition with dienes. The [4 + 4] cycloaddition is catalyzed by a quinine-derived primary amine in combination with a chiral phosphoric acid and a carboxylic acid affording cyclooctanoids isolated as a single diastereoisomer in good yields and with up to 94% ee. This reaction concept allows for the formation of cyclooctanoids without benzofusion, as demonstrated by oxidative opening of the furan ring. Computational studies of the reaction mechanism for the [4 + 4] cycloaddition point to a stepwise process. Surprisingly, the stereochemical outcome of the reaction is attributed to protonation of the two organocatalyst-bound cyclooctanoid intermediates leading to a preferred set-up for catalyst elimination to account for the absolute configuration of the cyclooctanoid.

Furfuryl alcohol is shown to serve as a biomass-based cosolvent par excellence for the alkaline hydrolysis of poly(ethylene terephthalate) (PET) bottle and PBA-PC compact disk waste. The solvent can be recycled, used at low levels (3 mL g⁻¹ PET), and operates in tandem with an efficient phase transfer catalyst to completely depolymerize PET at <100 °C in 10 min.

The rapid hydrolysis of poly(ethylene terephthalate) (PET) waste using sodium hydroxide, a phase transfer catalyst and furfuryl alcohol is demonstrated in 10 min at 98.5 °C. The cosolvent is biodegradable, available from biomass-based sources and outperforms a range of commonly used protic and polar aprotic cosolvents. Such is the competence of the cosolvent for this purpose that waste is minimized—for the first time minimal hydroxide (2.1 eq.) is employed and the solvent volume is limited to just 3 mL g⁻¹ PET (of which only 20% by weight is the organic component). It is found that the medium is compatible with phase transfer catalysis and a promoter incorporating aromatic units is superior (at 1 mol% loading) to previously optimal dimethyldialkylammonium halides. The medium can be recycled and reused after distillation at <100 °C, and furfuryl alcohol is also shown to serve as a cosolvent par excellence for the catalytic hydrolysis of poly(bis-phenol A carbonate) waste from compact disks under literature conditions.