Introduction of 3-indolylmethyl residues in nitroacetic acid esters

A method for the monoalkylation of nitroacetic ester with gramine in the presence of triethylamine is proposed. The basis of the method is the difference in the acidity of the nitroacetic acid ester and its monoalkylation product. The synthesis of -(3-indolyl)--R--nitropropionic acid esters (R=Me, Ph), which are precursors of -substituted tryptophans, was accomplished for the first time by alkylation of nitroacetic ester with indole Mannich bases containing alkyl or aryl substituents in the methylene group.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 780–784, June, 1978.     

DNAzyme- and light-induced dissipative and gated DNA networks

Nucleic acid-based dissipative, out-of-equilibrium systems are introduced as functional assemblies emulating transient dissipative biological transformations. One system involves a Pb²⁺-ion-dependent DNAzyme fuel strand-driven network leading to the transient cleavage of the fuel strand to “waste” products. Applying the Pb²⁺-ion-dependent DNAzyme to two competitive fuel strand-driven systems yields two parallel operating networks. Blocking the competitively operating networks with selective inhibitors leads, however, to gated transient operation of dictated networks, yielding gated catalytic operations. A second system introduces a “non-waste” generating out-of-equilibrium, dissipative network driven by light. The system consists of a trans-azobenzene-functionalized photoactive module that is reconfigured by light to an intermediary state consisting of cis-azobenzene units that are thermally recovered to the original trans-azobenzene-modified module. The cyclic transient photoinduced operation of the device is demonstrated. The kinetic simulation of the systems allows the prediction of the transient behavior of the networks under different auxiliary conditions.

Functional DNA modules are triggered in the presence of appropriate inhibitors to yield transient gated catalytic functions, and a photoresponsive DNA module leads to “waste-free” operation of transient, dissipative dynamic transitions.     

Fuel-driven macromolecular coacervation in complex coacervate core micelles

Fuel-driven macromolecular coacervation is an entry into the transient formation of highly charged, responsive material phases. In this work, we used a chemical reaction network (CRN) to drive the coacervation of macromolecular species readily produced using radical polymerisation methods. The CRN enables transient quaternization of tertiary amine substrates, driven by the conversion of electron deficient allyl acetates and thiol or amine nucleophiles. By incorporating tertiary amine functionality into block copolymers, we demonstrate chemical triggered complex coacervate core micelle (C3M) assembly and disassembly. In contrast to most dynamic coacervate systems, this CRN operates at constant physiological pH without the need for complex biomolecules. By varying the allyl acetate fuel, deactivating nucleophile and reagent ratios, we achieved both sequential signal-induced C3M (dis)assembly, as well as transient non-equilibrium (dis)assembly. We expect that timed and signal-responsive control over coacervate phase formation at physiological pH will find application in nucleic acid delivery, nano reactors and protocell research.

We apply an allyl acetate fuelled chemical reaction network (CRN) to control the coacervation of macromolecular species at constant physiological pH without the need for complex biomolecules.     

Biocatalytic reversible control of the stiffness of DNA-modified responsive hydrogels: applications in shape-memory,self-healing and autonomous controlled release of insulin

The enzymes glucose oxidase (GOx), acetylcholine esterase (AchE) and urease that drive biocatalytic transformations to alter pH, are integrated into pH-responsive DNA-based hydrogels. A two-enzyme-loaded hydrogel composed of GOx/urease or AchE/urease and a three-enzyme-loaded hydrogel composed of GOx/AchE/urease are presented. The biocatalytic transformations within the hydrogels lead to the dictated reconfiguration of nucleic acid bridges and the switchable control over the stiffness of the respective hydrogels. The switchable stiffness features are used to develop biocatalytically guided shape-memory and self-healing matrices. In addition, loading of GOx/insulin in a pH-responsive DNA-based hydrogel yields a glucose-triggered matrix for the controlled release of insulin, acting as an artificial pancreas. The release of insulin is controlled by the concentrations of glucose, hence, the biocatalytic insulin-loaded hydrogel provides an interesting sense-and-treat carrier for controlling diabetes.

Biocatalytic control over the stiffness of pH-responsive hydrogels is applied to develop shape-memory, self-healing and controlled release matrices.     

Organocatalytic cycloaddition–elimination cascade for atroposelective construction of heterobiaryls

The first chiral phosphoric acid (CPA) catalyzed cycloaddition–elimination cascade reaction of 2-naphthol- and phenol-derived enecarbamates with azonaphthalenes has been established, providing a highly atroposelective route to an array of axially chiral aryl-C3-benzoindoles in excellent yields with excellent enantioselectivities. The success of this strategy derives from the stepwise process involving CPA-catalyzed asymmetric formal [3 + 2] cycloaddition and subsequent central-to-axial chirality conversion by elimination of a carbamate. In addition, the practicality of this reaction had been verified by varieties of transformations towards functionalized atropisomers.

An organocatalytic asymmetric cycloaddition–elimination cascade reaction of aryl enecarbamates with azonaphthalenes has been developed to access axially chiral heterobiaryls in excellent yields and enantioselectivities.     

Bidentate substrate binding in Brønsted acid catalysis: structural space,hydrogen bonding and dimerization

BINOL derived chiral phosphoric acids (CPAs) are a prominent class of catalysts in the field of asymmetric organocatalysis, capable of transforming a wide selection of substrates with high stereoselectivities. Exploiting the Brønsted acidic and basic dual functionality of CPAs, substrates with both a hydrogen bond acceptor and donor functionality are frequently used as the resulting bidentate binding via two hydrogen bonds is expected to strongly confine the possible structural space and thus yield high stereoselectivities. Despite the huge success of CPAs and the popularity of a bidentate binding motif, experimental insights into their organization and origin of stereoinduction are scarce. Therefore, in this work the structural space and hydrogen bonding of CPAs and N-(ortho-hydroxyaryl) imines (19 CPA/imine combinations) was elucidated by low temperature NMR studies and corroborated by computations. The postulated bidentate binding of catalyst and substrate by two hydrogen bonds was experimentally validated by detection of trans-hydrogen bond scalar couplings. Counterintuitively, the resulting CPA/imine complexes showed a broad potential structural space and a strong preference towards the formation of [CPA/imine]₂ dimers. Molecular dynamics simulations showed that in these dimers, the imines form each one hydrogen bond to two CPA molecules, effectively bridging them. By finetuning steric repulsion and noncovalent interactions, rigid and well-defined CPA/imine monomers could be obtained. NOESY studies corroborated by theoretical calculations revealed the structure of that complex, in which the imine is located in between the 3,3′-substituents of the catalyst and one site of the substrate is shielded by the catalyst, pinpointing the origin or stereoselectivity for downstream transformations.

Brønsted acid/substrate complexes with bidentate binding motif were studied by NMR and molecular dynamics. A variety of different arrangements was found, including bridged dimers and monomers were characterised in detail.     

Kinetics and mechanism of benzyl <Emphasis Type="Italic">para</Emphasis>-chlorophenyl ketone oxidation

The oxidation of benzyl para-chlorophenyl ketone in chlorobenzene at 100°C occurs through the formation of short chains. Non-peroxide reaction products (1-(4-chlorophenyl)-2-hydroxy-2-phenyl-1-ethanone, para-chlorobenzyl, benzaldehyde, and para-chlorobenzoic acid) are formed not only by the transformation of hydroperoxide (1-(4-chlorophenyl)-2-hydroxy-2-phenyl-1-ethanone) but also (or solely) through the recombination of α-ketoperoxyl radicals with or without chain termination. α-Hydroperoxide decomposes predominantly through a heterolytic route to form para-chlorobenzoic acid and benzaldehyde. Benzaldehyde and 1-(4-chlorophenyl)-2-hydroxy-2-phenyl-1-ethanone undergo radical chain oxidation in the reaction medium to form benzoic acid (benzaldehyde), para-chlorobenzyl, and benzoic and para-chlorobenzoic acids (1-(4-chlorophenyl)-2-hydroxy-2-phenyl-1-ethanone). The homolytic decomposition of α-hydroperoxy ketone and α-hydroxy-α-hydroperoxy ketone causes the self-acceleration of the process and affords 1-(4-chlorophenyl)-2-hydroxy-2-phenyl-1-ethanone or, to a lesser extent, benzaldehyde and para-chlorobenzoic acid (α-hydroperoxy ketone). para-Chlorobenzoic acid substantially accelerates the heterolytic decomposition of α-hydroxy-α-hydroperoxy ketone and the oxidation of benzyl para-chlorophenyl ketone with peroxy acids to ester according to the Baeyer-Villiger mechanism. The rate constants of the main steps of the process and kinetic parameters are calculated by solving the inverse kinetic problem.     

A new twist for Stork-Danheiser products enabled by visible light mediated trans-cyclohexene formation; access to acyclic distal enones

Herein, we investigate the use of visible light to indirectly drive ring opening in unstrained 6- and 7-membered ring systems via reaction with a transiently generated trans-cycloalkene. Identification of conditions that capture visible light energy in the form of ring strain was key to success. Under mildly acidic conditions, cycloalkenols were shown to undergo formally endothermic ring-opening isomerization to give acyclic exo-methylene and distal ketones or aldehydes in high yields. Ultimately, this work demonstrates the ability of cycloalkenes to capture visible light energy and its use to drive both kinetically and thermally unfavorable rearrangements.

In this work, visible light drives a contrathermodynamic isomerization of the classic Stork-Danheiser products through an energy transfer process to yield acyclic distal enone(al) isomers. This is possible because the photochemical energy is transiently captured as ring strain as a trans-, or twisted, cyclohexene.     

Improving the intrinsic activity of electrocatalysts for sustainable energy conversion: where are we and where can we go?

As we are in the midst of a climate crisis, there is an urgent need to transition to the sustainable production of fuels and chemicals. A promising strategy towards this transition is to use renewable energy for the electrochemical conversion of abundant molecules present in the earth''s atmosphere such as H₂O, O₂, N₂ and CO₂, to synthetic fuels and chemicals. A cornerstone to this strategy is the development of earth abundant electrocatalysts with high intrinsic activity towards the desired products. In this perspective, we discuss the importance and challenges involved in the estimation of intrinsic activity both from the experimental and theoretical front. Through a thorough analysis of published data, we find that only modest improvements in intrinsic activity of electrocatalysts have been achieved in the past two decades which necessitates the need for a paradigm shift in electrocatalyst design. To this end, we highlight opportunities offered by tuning three components of the electrochemical environment: cations, buffering anions and the electrolyte pH. These components can significantly alter catalytic activity as demonstrated using several examples, and bring us a step closer towards complete system level optimization of electrochemical routes to sustainable energy conversion.

We evaluate the improvements over the past two decades in intrinsic activity of electrocatalysts for sustainable energy conversion, and highlight opportunities from tuning the electrolyte.     

Local detection of pH-induced disaggregation of biocompatible micelles by fluorescence switch ON

Fluorogenic nanoparticles (NPs) able to sense different physiological environments and respond with disaggregation and fluorescence switching OFF/ON are powerful tools in nanomedicine as they can combine diagnostics with therapeutic action. pH-responsive NPs are particularly interesting as they can differentiate cancer tissues from healthy ones, they can drive selective intracellular drug release and they can act as pH biosensors. Controlled polymerization techniques are the basis of such materials as they provide solid routes towards the synthesis of pH-responsive block copolymers that are able to assemble/disassemble following protonation/deprotonation. Ring opening metathesis polymerization (ROMP), in particular, has been recently exploited for the development of experimental nanomedicines owing to the efficient direct polymerization of both natural and synthetic functionalities. Here, we capitalize on these features and provide synthetic routes for the design of pH-responsive fluorogenic micelles via the assembly of ROMP block-copolymers. While detailed photophysical characterization validates the pH response, a proof of concept experiment in a model cancer cell line confirmed the activity of the biocompatible micelles in relevant biological environments, therefore pointing out the potential of this approach in the development of novel nano-theranostic agents.

pH-responsive micelles disassembly, upon acidification during lysosomal uptake, leads to fluorescence switch ON. These nanoparticles are promising candidates for the design of novel stimuli-responsive drug delivery systems.     

Metal–organic frameworks as hypergolic additives for hybrid rockets

Hybrid rocket propulsion can contribute to reduce launch costs by simplifying engine design and operation. Hypergolic propellants, i.e. igniting spontaneously and immediately upon contact between fuel and oxidizer, further simplify system integration by removing the need for an ignition system. Such hybrid engines could also replace currently popular hypergolic propulsion approaches based on extremely toxic and carcinogenic hydrazines. Here we present the first demonstration for the use of hypergolic metal–organic frameworks (HMOFs) as additives to trigger hypergolic ignition in conventional paraffin-based hybrid engine fuels. HMOFS are a recently introduced class of stable and safe hypergolic materials, used here as a platform to bring readily tunable ignition and combustion properties to hydrocarbon fuels. We present an experimental investigation of the ignition delay (ID, the time from first contact with an oxidizer to ignition) of blends of HMOFs with paraffin, using White Fuming Nitric Acid (WFNA) as the oxidizer. The majority of measured IDs are under 10 ms, significantly below the upper limit of 50 ms required for functional hypergolic propellant, and within the ultrafast ignition range. A theoretical analysis of the performance of HMOFs-containing fuels in a hybrid launcher engine scenario also reveals the effect of the HMOF mass fraction on the specific impulse (I_sp) and density impulse (ρI_sp). The use of HMOFs to produce paraffin-based hypergolic fuels results in a slight decrease of the I_sp and ρI_sp compared to that of pure paraffin, similar to the effect observed with Ammonia Borane (AB), a popular hypergolic additive. HMOFs however have a much higher thermal stability, allowing for convenient mixing with hot liquid paraffin, making the manufacturing processes simpler and safer compared to other hypergolic additives such as AB.

Hypergolic hybrid rocket propulsion, achieved through the addition of metal–organic frameworks, can contribute to reduce launch costs by simplifying engine design and operation.     

Baseline studies of the global pollution

Summary Fish and fish oils, which can be assigned to defined food webs, habitats and regions in the North Atlantic (Gulf Stream, Sargasso Sea, continental shelf of Iceland, Ireland, Norway, North Sea and Portugal) have been analyzed for organochloro compounds like hexachlorocyclohexane isomers (HCH), chloroterpene (toxaphen, polychlorocamphene), cyclodien pesticides (chlordane group, dieldrin), chlorobenzenes, chlorobiphenyls (PCB) and the DDT group. Phytoplancton feeding fish menhaden (Brevoortia tyrannus) were used to characterize the surface layer of the Atlantic west of the United States, while ground feeding predatory cod (Gadus morhua) and sea pike (Merluccius merluccius) should picture mainly the pollution near the continental shelf at 200–600 m depth.All groups of chemicals listed above could be found in the fish samples and in most cases the single components of mixtures (PCB, chlordane) could be identified by high resolution glass capillary gas chromatography with electron capture detection. Intensity and details of the pollution pattern vary strongly for the water regions investigated. The global water cycle and details of pollution input and history of water bodies can be used for an explanation.

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Untersuchungen zur globalen Belastung der UmweltIV. Belastungsmuster der Organochlorverbindungen im Nordatlantik, angereichert in Fischen

Zusammenfassung In Fischen, die einer bestimmten Nahrungskette und Region zuzuordnen sind (Bermuda, Kontinentalschelf westlich von Irland und Portugal) und in Dorschleberölen, die aus definierten Regionen des Nordatlantiks (Kontinentschelf von Island, Irland, Norwegen, Nordsee und Portugal) stammen, wurde die Belastung mit Hexachlorcyclohexanen (HCH), Chlorterpenen (Toxaphen), Cyclodien-Biociden (Chlordan-Gruppe, Dieldrin), Chlorbenzolen, Chlorbiphenylen (PCB) und der DDT-Gruppe bestimmt. Im Oberflächenwasser lebende Phytoplanktonfiltrierer [Menhaden (Brevoortia tyrannus)] wie auf dem Schelfsockel lebende bathypelagische Räuber [Dorsch, Kabeljau (Gadus morhua) und Seehecht (Merluccius merluccius)] sind untersucht worden. Damit ist der Eintrag sowohl nahezu unmittelbar aus dem Wasser (Phytoplanktonfiltrierer) wie über eine längere mittelbare und unmittelbare Nahrungskette (bathypelagische Räuber), erfaßt worden. Alle aufgeführten Substanzklassen konnten z. T. mit weitgehender Identifizierung der Einzelkomponenten durch hochauflösende Glas-Capillar-Gas-Chromatographie und Elektroneneinfang-Detektion nachgewiesen werden. Es zeigen sich deutliche regionale Unterschiede in der Stärke der Belastung und in dem Belastungsmuster. Die globale Wasserführung und der damit verbundene unterschiedliche Eintrag wie die unterschiedliche Historie der Wassermassen können als Erklärung herangezogen werden.

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List of Abbreviations PCBZ Polychlorobenzene - TrCBZ Trichlorobenzene - PeCBZ Pentachlorobenzene - HCH Hexachlorocyclohexane - PCB Polychlorobiphenyl - 1-209 Polychlorobiphenyl of defined structure [4] - B Polychlorobiphenyl of undefined structure - DDT Dichlorodiphenyl-trichloroethane - 2,4-DDT 1,1,1-Trichloro-2-(2-chlorophenyl)-2-(4-chlorophenyl)-ethane - 2,4-DDD 1,1-Dichloro-2-(2-chlorphenyl)-2-(4-chlorophenyl)-ethane - 2,4-DMD 1-Chloro-2-(2-chlorophenyl)-2-(4-chlorophenyl)-ethane - 2,4-DDE 1,1-Dichloro-2-(2-chlorophenyl)-2-(4-chlorophenyl)-ethene - 2,4-DDMU 1-Chloro-2-(2-chlorophenyl)-2-(4-chlorophenyl)-ethene - 2,4-DBP 2,4-Dichloro-benzophenone - 4,4-DDT 1,1,1-Trichloro-2,2-bis(4-chlorophenyl)-ethane - 4,4-DDD 1,1-Dichloro-2,2-bis(4-chlorophenyl)-ethane - 4,4-DMD 1-Chloro-2,2-bis(4-chlorophenyl)-ethane - 4,4-DDE 1,1-Dichloro-2,2-bis(4-chlorphenyl)ethene - 4,4-DDMU 1-Chloro-2,2-bis(4-chlorophenyl)-ethene - 4,4-DBP 4,4-Dichloro-benzophenone - CY Dieldrin Endrin Cyclodien-biocides - Hepo Heptachloroepoxid - CY 40 cis-Chlordane - CY 41 trans-Chlordane - CY 50 cis-Nonachlor - CY 51 trans-Nonachlor - PCT(T) Polychloroterpene (Toxaphene, Polychlorocamphen, Strobane) - U Major unknowns/not identified compounds     

Reaction of 2-aryl-1,3-dioxolanes with nitroacetic ester

Conclusions 2-Phenyl-1,3-dioxolane, and its derivatives with donor substituents in the aromatic ring, react with the methyl ester of nitroacetic acid in Ac₂O medium and in the presence of acid catalysts to give the methyl esters of the corresponding -nitrocinnamic acids.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 439–440, February, 1982.     

An in situ masking strategy enables radical monodecarboxylative C–C bond coupling of malonic acid derivatives

The utilization of malonic acids in radical decarboxylative functionalization is still underexploited, and the few existing examples are primarily limited to bisdecarboxylative functionalization. While radical monodecarboxylative functionalization is highly desirable, it is challenging because of the difficulty in suppressing the second radical decarboxylation step. Herein, we report the successful radical monodecarboxylative C–C bond coupling of malonic acids with ethynylbenziodoxolone (EBX) reagents enabled by an in situ masking strategy, affording synthetically useful 2(3H)-furanones in satisfactory yields. The keys to the success of this transformation include (1) the dual role of a silver catalyst as a single-electron transfer catalyst to drive the radical decarboxylative alkynylation and as a Lewis acid catalyst to promote the 5-endo-dig cyclization and (2) the dual function of the alkynyl reagent as a radical trapper and as an in situ masking group. Notably, the latent carboxylate group in the furanones could be readily released, which could serve as a versatile synthetic handle for further elaborations. Thus, both carboxylic acid groups in malonic acid derivatives have been well utilized for the rapid construction of molecular complexity.

An in situ masking strategy has been developed based upon the unique properties of silver catalysts to successfully achieve a radical monodecarboxylative C–C bond coupling of malonic acids with ethynylbenziodoxolone reagents.     

Direct discrimination of cell surface glycosylation signatures using a single pH-responsive boronic acid-functionalized polymer

Cell surface glycans serve fundamental roles in many biological processes, including cell–cell interaction, pathogen infection, and cancer metastasis. Cancer cell surface have alternative glycosylation to healthy cells, making these changes useful hallmarks of cancer. However, the diversity of glycan structures makes glycosylation profiling very challenging, with glycan ‘fingerprints’ providing an important tool for assessing cell state. In this work, we utilized the pH-responsive differential binding of boronic acid (BA) moieties with cell surface glycans to generate a high-content six-channel BA-based sensor array that uses a single polymer to distinguish mammalian cell types. This sensing platform provided efficient discrimination of cancer cells and readily discriminated between Chinese hamster ovary (CHO) glycomutants, providing evidence that discrimination is glycan-driven. The BA-functionalized polymer sensor array is readily scalable, providing access to new diagnostic and therapeutic strategies for cell surface glycosylation-associated diseases.

A high-content multichannel sensor array was developed to efficiently discriminate cell states. The binding of boronic acid with glycans is pH-responsive, hence utilizing three pH provides a sensitive multidimensional array from a single polymer.     

Surface-controlled spatially heterogeneous physical properties of a supramolecular gel with homogeneous chemical composition

Controlling supramolecular self-assembly across multiple length scales to prepare gels with localised properties is challenging. Most strategies concentrate on fabricating gels with heterogeneous components, where localised properties are generated by the stimuli-responsive component. Here, as an alternative approach, we use a spiropyran-modified surface that can be patterned with light. We show that light-induced differences in surface chemistry can direct the bulk assembly of a low molecular weight gelator, 2-NapAV, meaning that mechanical gel properties can be controlled by the surface on which the gel is grown. Using grazing incidence X-ray diffraction and grazing incidence small angle X-ray scattering, we demonstrate that the origin of the different gel properties relates to differences in the architectures of the gels. This provides a new method to prepare a single domain (i.e., chemically homogeneous) hydrogel with locally controlled (i.e., mechanically heterogeneous) properties.

A mechanical pattern is created in a hydrogel film by pre-patterning the underlying surface chemistry. This allows spatial variation of the viscous component of the gel, controlling dissipative forces in the gel film without altering gel chemistry.     

Imaging of hypochlorous acid in mitochondria using an asymmetric near-infrared fluorescent probe with large Stokes shift

Small-molecule near-infrared (NIR) imaging facilitates deep tissue penetration, low autofluorescence, non-invasive visualization, and a relatively simple operation. As such it has emerged as a popular technique for tracking biological species and events. However, the small Stokes shift of most NIR dyes often results in a low signal-to-noise ratio and self-quenching due to crosstalk between the excitation and emission spectra. With this research, we developed a NIR-based fluorescent probe WD-HOCl for hypochlorous acid (HOCl) detection using the NIR dye TJ730 as the fluorophore, which exhibits a large Stokes shift of 156 nm, with no crosstalk between the excitation and emission spectra. It contains acyl hydrazide as the responsive group and a pyridinium cation as the mitochondria-targeting group. The fluorescence intensity of WD-HOCl was enhanced by 30.1-fold after reacting with HOCl. Imaging studies performed using BV-2 cells indicated that WD-HOCl could be used for endogenous HOCl detection and imaging in living cells exposed to glucose and oxygen deprivation/reperfusion. Finally, we demonstrated that inhibiting the expression of NOX2 reduced the HOCl levels and the severity of oxidative stress during stroke in a mouse model.

Small-molecule near-infrared (NIR) imaging facilitates deep tissue penetration, low autofluorescence, non-invasive visualization, and a relatively simple operation.     

Light-driven redox deracemization of indolines and tetrahydroquinolines using a photocatalyst coupled with chiral phosphoric acid

The integration of oxidation and enantioselective reduction enables a redox deracemization to directly access enantioenriched products from their corresponding racemates. However, the solution of the kinetically microscopic reversibility of substrates used in this oxidation/reduction unidirectional event is a great challenge. To address this issue, we have developed a light-driven strategy to enable an efficient redox deracemization of cyclamines. The method combines a photocatalyst and a chiral phosphoric acid in a toluene/aqueous cyclodextrin emulsion biphasic co-solvent system to drive the cascade out-of-equilibrium. Systemic optimizations achieve a feasible oxidation/reduction cascade sequence, and mechanistic investigations demonstrate a unidirectional process. This single-operation cascade route, which involves initial photocatalyzed oxidation of achiral cyclamines to cyclimines and subsequent chiral phosphoric acid-catalyzed enantioselective reduction of cyclimines to chiral cyclamines, is suitable for constructing optically pure indolines and tetrahydroquinolines.

A light-driven redox deracemization to prepare optically pure cyclamines from their racemates is developed. This reaction provides a wide range of chiral indolines and tetrahydroquinolines with high yields and enantioselectivities.     

Enantioselective crossed intramolecular [2+2] photocycloaddition reactions mediated by a chiral chelating Lewis acid

In intramolecular [2+2] photocycloaddition reactions, the two tethered olefins can approach each other in a straight or in a crossed fashion. Despite the fact that the latter reaction mode leads to intriguing, otherwise inaccessible bridged skeletons, there has so far not been any enantioselective variants thereof. This study concerned the crossed [2+2]-photocycloaddition of 2-(alkenyloxy)cyclohex-2-enones to bridged cyclobutanes. It was found that the reaction could be performed with high enantioselectivity (80–94% ee) under visible light conditions when employing a chiral rhodium Lewis acid as a catalyst (2 mol%).

An enantioselective crossed [2+2] photocycloaddition is presented which proceeds under visible light irradiation in the presence of a chiral Lewis acidic metal complex. Chelation of two oxygen atoms to the metal centre accounts for the observed enantioface differentiation.