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The practical aspects of some NMR experiments designed for the simultaneous acquisition of 2D COSY and 2D TOCSY spectra are presented and discussed. Several techniques involving afterglow‐based, coherence transfer pathway (CTP)‐based, and NMR by Ordered Acquisition using 1H‐detection (NOAH)‐based strategies for the collection of different free‐induction signal decays (FIDs) within the same scan are evaluated and compared. These methods offer a faster recording of these spectra in small‐molecule NMR when sensitivity is not a limiting factor, with a reduction in spectrometer time about 45–60% when compared with the conventional sequential acquisition of the parent experiments. It is also shown how the optimized design of an extended three‐FID approach yields one COSY and two TOCSY spectra simultaneously by combining CTP and NOAH principles in the same experiment, affording substantial sensitivity enhancements per time unit. The practical aspects of some pulse sequences designed for the simultaneous acquisition of 2D COSY and 2D TOCSY spectra are presented and discussed. Several techniques have been developed for the collection of two and three different FIDs within the same scan (MFA). These time‐efficient methods offer a faster recording of these spectra when sensitivity is not a limiting factor, with a reduction in spectrometer time about 45–60% when compared with the conventional sequential acquisition of the parent experiments. [ABSTRACT FROM AUTHOR]

The development of new tools to improve the quality of nuclear magnetic resonance (NMR) spectra is a challenging task. The concept of "perfect NMR" includes the design of robust pulse sequences that allow an investigator to obtain undistorted pure in‐phase signals, with pure absorption lineshapes that are free of phase anomalies derived from undesired J modulations. Here, alternative NMR building blocks to the spin‐echo that are based on a general double SE module, known as a perfect‐echo, are reviewed. Several implementations to minimize/remove unwanted dispersive contributions in homonuclear and heteronuclear NMR experiments are described and illustrated with some examples of broad interest for small molecules. The concept of "perfect NMR" includes the design of robust pulse sequences that allow obtaining undistorted pure in‐phase signals, with pure absorption lineshapes and free of phase anomalies derived from undesired J modulations. Here, alternative NMR building blocks to spin‐echo which are based on a general double SE module, known as perfect‐echo, are reviewed. Several implementations to minimize/remove unwanted dispersive contributions in homonuclear and heteronuclear NMR experiments are described and illustrated with some examples of broad interest for small molecules. [ABSTRACT FROM AUTHOR]

A 1H‐1H total correlation spectroscopy (TOCSY) experiment incorporating 13C multiplicity information is proposed. In addition, broadband 1H homodecoupling in the indirect dimension can be implemented using a perfect BIRD module that affords exclusive 1H chemical shift evolution with full decoupling of all heteronuclear and homonuclear (including 2JHH) coupling constants. As a complement to the normal TOCSY and the recent PSYCHE‐TOCSY experiments, this novel multiplicity‐edited TOCSY experiment distinguishes between CH/CH3 (phased up) and CH2 (phased down) cross‐peaks, which facilitates resonance analysis and assignment. [ABSTRACT FROM AUTHOR]

Two‐dimensional J‐resolved (Jres) NMR experiments offer a simple, user‐friendly spectral representation where the information of coupling constants and chemical shifts are separated into two orthogonal frequency axis. Since its initial proposal 40 years ago, Jres has been the focus of considerable interest both in improving the basic pulse sequence and in its successful application to a wide range of studies. Here, the latest developments in the design of novel Jres pulse schemes are reviewed, mainly focusing on obtaining pure absorption lineshapes, minimizing strong coupling artifacts, and also optimizing sensitivity and experimental measurements. A discussion of several Jres versions for the accurate measurement of a different number of homonuclear (JHH) and heteronuclear (JCH) coupling constants is presented, accompanied by some illustrative examples. [ABSTRACT FROM AUTHOR]

Allene-( E)-ene-yne N-tosyl-tethered substrates 3 a- 3 h were efficiently prepared and their rhodium-catalyzed [2+2+2] cycloaddition reactions were evaluated. The cycloadditions are chemoselective as only the proximal double bond of the allene reacted to afford exocyclic double bonds in the fused-tricyclic scaffolds. The stereoselectivity depended on the catalytic system used. Reactivity between allene, alkene, and alkyne was studied for the first time by density functional theory calculations. This mechanistic study determines the order in which the unsaturated groups take part in the catalytic cycle. [ABSTRACT FROM AUTHOR]

Intramolecular benzoin reactions catalyzed by benzaldehyde lyase from Pseudomonas fluorescens biovar I (BAL) are reported. The structure of the substrates envisaged for this reaction consists of two benzaldehyde derivatives linked by an alkyl chain. The structural requirements needed to achieve the intramolecular carbon-carbon bond reaction catalyzed by BAL were established. Thus, a linker consisting of a linear alkyl chain of three carbon atoms connected through ether-type bonds to the 2 and 2′ positions of two benzaldehyde moieties, which could be substituted with either Cl, Br, or OCH3 at either the 3 and 3′ or 5 and 5′ positions, were suitable substrates for BAL. Reactions with 61-84 % yields of the intramolecular product and ee values between 64 and 98 %, were achieved. [ABSTRACT FROM AUTHOR]

Intramolecular benzoin reactions catalyzed by benzaldehyde lyase from Pseudomonas fluorescens biovar I (BAL) are reported. The structure of the substrates envisaged for this reaction consists of two benzaldehyde derivatives linked by an alkyl chain. The structural requirements needed to achieve the intramolecular carbon-carbon bond reaction catalyzed by BAL were established. Thus, a linker consisting of a linear alkyl chain of three carbon atoms connected through ether-type bonds to the 2 and 2′ positions of two benzaldehyde moieties, which could be substituted with either Cl, Br, or OCH3 at either the 3 and 3′ or 5 and 5′ positions, were suitable substrates for BAL. Reactions with 61-84 % yields of the intramolecular product and ee values between 64 and 98 %, were achieved. [ABSTRACT FROM AUTHOR]

Homonuclear 13C-13C couplings at natural abundance can be measured using the J-modulated Adequate DoublE QUAntumTransfer Experiment (ADEQUATE) experiment. To somewhat ameliorate F1 digitization requirements, a scaling factor was incorporated into the original pulse sequence. Non-uniform sampling provides an obvious avenue to further facilitate the acquisition of 1 JCC and n JCC homonuclear coupling constant data. We introduce homonuclear decoupling (HD) analogous to that described for the 1,1-HD-ADEQUATE and 1,n-HD-ADEQUATE experiments and evaluate the combination of non-uniform sampling and HD on the acquisition of both 1 JCC and n JCC homonuclear 13C-13C coupling constants using ibuprofen as a model compound. Copyright © 2015 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

The reaction of diyne arylsulfonyl hydrazone substrates under rhodium(I)/BINAP catalysis gives access to sulfonated azacyclic frameworks in a highly enantioselective manner. This new cascade process considerably increases the molecular complexity by generating two CC bonds, one CS bond, and one CH bond. Theoretical calculations, competitive experiments, and deuterium labeling have jointly been used to propose a mechanism that accounts for the reaction. The mechanism involves the formation of vinyl rhodium carbenoids, hydride migratory insertion, and intermolecular stereoselective nucleophilic attack. The last two steps are the key to the stereoselectivity of the process. [ABSTRACT FROM AUTHOR]

In recent years, a great interest in the development of new broadband 1H homonuclear decoupled techniques providing simplified JHH multiplet patterns has emerged again in the field of small molecule NMR. The resulting highly resolved 1H NMR spectra display resonances as collapsed singlets, therefore minimizing signal overlap and expediting spectral analysis. This review aims at presenting the most recent advances in pure shift NMR spectroscopy, with a particular emphasis to the Zangger-Sterk experiment. A detailed discussion about the most relevant practical aspects in terms of pulse sequence design, selectivity, sensitivity, spectral resolution and performance is provided. Finally, the implementation of the different reported strategies into traditional 1D and 2D NMR experiments is described while several practical applications are also reviewed. Copyright © 2015 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

NMR-aided enantiodiscrimination using chiral auxiliaries (CAs) is a recognized method for differentiating enantiomers and for measuring enantiomeric ratios (er). Up to the present, the study, optimization, and comparison of such methods have been performed based on the enantiodifferentiation of NMR signals via analyzing non-equivalent chemical-shift values (ΔΔ δ ) of the diastereoisomeric species formed. However, a poor and non-reliable comparison of results is often obtained via the analysis of ΔΔ δ exclusively. In here, the concept of enantioresolution of an individual NMR signal and its importance for NMR-aided enantiodifferentiation studies is introduced and discussed. In addition, the enantioresolution quotient, E , is proposed as the parameter to describe its quantification. Complementary to measuring ΔΔ δ , the experimental determination of E allows a more reliable interpretation of the results and opens up new possibilities for the study of enantiodifferentiation data derived from novel NMR experiments, setup improvements or new CAs. Finally, the different relationships between signal enantiodifferentiation, signal enantioresolution, and other main experimental issues of enantiodifferentiation experiments are addressed. [ABSTRACT FROM AUTHOR]

The introduction of aromatic residues connected by a CC bond into the non-reducing end of carbohydrates is highly significant for the development of innovative structures with improved binding affinity and selectivity (e.g., Caril-sLex). In this work, an expedient asymmetric 'de novo' synthetic route to new aryl carbohydrate derivatives based on two sequential stereoselectively biocatalytic carboligation reactions is presented. First, the benzoin reaction of aromatic aldehydes to dimethoxyacetaldehyde is conducted, catalyzed by benzaldehyde lyase from Pseudomonas fluorescens biovar I. Then, the α-hydroxyketones formed are reduced by using NaBH4 yielding the anti diol. After acetal hydrolysis, the aldol addition of dihydroxyacetone, hydroxyacetone, or glycolaldehyde catalyzed by the stereocomplementary D-fructose-6-phosphate aldolase and L-rhamnulose-1-phosphate aldolase is performed. Both aldolases accept unphosphorylated donor substrates, avoiding the need of handling the phosphate group that the dihydroxyacetone phosphate-dependent aldolases require. In this way, 6- C-aryl- L-sorbose, 6- C-aryl- L-fructose, 6- C-aryl- L-tagatose, and 5- C-aryl- L-xylose derivatives are prepared by using this methodology. [ABSTRACT FROM AUTHOR]

The effects of phase modulation due to homonuclear proton-proton coupling constants in HSQMBC-IPAP and HMBC-IPAP experiments are experimentally evaluated. We show that accurate values of small proton-carbon coupling constants, nJCH, can be extracted even for phase-distorted cross-peaks obtained from a selHSQMBC experiment applied simultaneously on two mutually J-coupled protons. On the other hand, an assessment of the reliability of nJCH measurement from distorted cross-peaks obtained in broadband IPAP versions of equivalent HMBC and HSQMBC experiments is also presented. Finally, we show that HMBC-COSY experiments could be an excellent complement to HMBC for the measurement of small nJCH values. Copyright © 2013 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Three different J-editing methods (IPAP, E.COSY and J-resolved) are implemented in a single NMR experiment to provide spin-state-edited 2D cross-peaks from which a simultaneous measurement of different homonuclear and heteronuclear coupling constants can be performed. A new J-selHSQMBC-IPAP experiment is proposed for the independent measurement of two different nJ(CH) coupling constants along the F2 and F1 dimensions of the same 2D cross-peak. In addition, the E.COSY pattern provides additional information about the magnitude and relative sign between J(HH) and nJ(CH) coupling constants. Copyright © 2013 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

A well-defined macrocyclic aryl-CuIIIcomplex(1) readily reacts with a series of R–SH, Ar–SH,Ar–SeH, and (RO)2(O)–PH (R = alkyl) nucleophilesto quantitatively afford the corresponding aryl alkyl thioethers,biaryl thioethers, biaryl selenide, and aryl dialkyl phosphonates,respectively. Competition experiments using bifunctional substratesrevealed the important impact of lower pKavalues in order to discriminate between functional groups, althoughother influencing parameters such as steric effects have been identified.The catalytic version of these reactions is achieved using aryl bromideand aryl chloride model substrates, affording C–S, C–Se,and C–P coupling compounds in excellent to moderate yields.Low-temperature UV–vis and NMR monitoring of the reactionsof complex 1with a variety of nucleophiles support theformation of a ground-state 1–nucleophile adduct.A mechanistic proposal for reaction of 1with S-nucleophilesinvolving key nucleophile deprotonation and aryl-nucleophile reductiveelimination steps is finally described. [ABSTRACT FROM AUTHOR]

A spin state-selective Heteronuclear Single-Quantum Multiple-Bond Connectivities (HSQMBC-COSY) experiment is proposed to measure the sign and the magnitude of long-range proton-carbon coupling constants ( nJ(CH); n > 1) either for protonated or for non-protonated carbons in small molecules. The simple substitution of the selective 180° 1H pulse in the original selHSQMBC pulse scheme by a hard one allows the simultaneous evolution of both proton-proton and proton-carbon coupling constants during the refocusing period and enables a final COSY transfer between coupled protons. The successful implementation of the IPAP principle leads to separate mixed-phase α/β cross-peaks from which nJ(CH) values can be easily measured by analyzing their relative frequency displacements in the detected dimension. Copyright © 2012 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

The feasibility of degrading triphenylmethane dyes by Trametes versicolor and laccase has been investigated for the following dyes: Acid Fuchsin, Brilliant Green 1, Basic Fuchsin, Methyl Green or Acid Green 16. The toxicity level of triphenylmethane dyes is linked to their basic character, but significant detoxification is obtained when there is biodegradation. Identification of enzymatic degradation products by 1H NMR made it possible to propose a general rule for the laccase attack on triphenylmethane compounds. The enzyme completely degrades the molecular part of the canonical resonance substructures of dyes, because no N-substituted, mono-N and di-N,N substituted p-amine aromatic residues seem to be wholly degraded. No enzymatic degradation is observed in the cases of either the non-substituted or trisubstituted-N,N,N p-amine aromatic residues. On the other hand, for all the dyes tested, no aromatic residues are detected after fungal treatment; this means that T. versicolor is more capable of performing further degradation than is laccase. The results of this study demonstrated that compounds with a triphenylmethane structure can be degraded by T. versicolor even if they are highly toxic. The enzyme laccase plays an important role in the attack on the structure and a general rule for predicting which products would be obtained after the enzymatic treatment is suggested. [Copyright &y& Elsevier]

Abstract: For the first time, a simple NMR methodology is proposed for the accurate determination of the effect of the substitution of 12C by 13C on the chemical shifts of protons separated by two-bonds in small molecules in their natural abundance. [Copyright &y& Elsevier]

The white-rot fungus Trametes versicolor degraded trichloroethylene (TCE), a highly oxidized chloroethene, and produced 2,2,2-trichloroethanol and carbon dioxide as the main products of degradation, based on the results obtained using [13C]-TCE as the substrate. For a range of concentrations of TCE between 2 and 20mgl−1, 53% of the theoretical maximum chloride expected from complete degradation of TCE was observed. Laccase was shown to be induced by TCE, but did not appear to play a role in TCE degradation. Cytochrome P-450 appears to be involved in TCE degradation, as evidenced by marked inhibition of degradation of TCE in the presence of 1-aminobenzotriazole, a known inhibitor of cytochrome P-450. Our results suggested that chloral (trichloroacetaldehyde) was an intermediate of the TCE degradation pathway. The results indicate that the TCE degradation pathway in T. versicolor appears to be similar to that previously reported in mammals and is mechanistically quite different from bacterial TCE degradation. [Copyright &y& Elsevier]

Abstract: Simple modifications of the sensitivity-improved HSQC–TOCSY pulse sequence are proposed for the easy determination of the sign and the magnitude of homonuclear and heteronuclear coupling constants. Whereas in well-resolved regions, a clean two-component E.COSY-like pattern allows a direct measurement from a single 2D spectrum, separate acquisition of equivalent single-component TROSY/anti-TROSY spectra becomes highly interesting when spectral crowding complicates the spectral analysis. It is also demonstrated that an additional restricted planar mixing element after the isotropic TOCSY process completely retains all spin-editing features and permits the accurate measurement of the sign and the size of the corresponding homonuclear proton–proton coupling constants. Among others, the proposed techniques are particularly suited for molecules presenting a great number of CH and NH spin systems. Examples and practical details of the implementation of these techniques on standard carbohydrates and peptides at 13C and 15N natural abundance are provided. [Copyright &y& Elsevier]

Several heteronuclear coherence transfer mechanisms involved in proton-detected heteronuclear J-cross-polarization (HCP) NMR experiments have been theoretically derived and experimentally verified in isotropic solution. It is shown that in-phase and/or anti-phase heteronuclear coherence transfer can take place separately or simultaneously during the HCP process as a function of the relative phase between the HCP mixing sequence and the corresponding input magnetization. As the more important consequence, clean coherence-order and spin-state selective (S3) excitation with maximum sensitivity can be achieved from gradient-enhanced HCP experiments by proper co-addition/subtraction of in-phase and anti-phase magnetizations, offering an attractive alternative to widely used HSQC-type experiments. [Copyright &y& Elsevier]

Water pollution threatens human and environmental health worldwide. Thus, there is a pressing need for new approaches to water purification. Herein, we report a novel supramolecular strategy based on the use of a metal‐organic polyhedron (MOP) as a capture agent to remove nitrogenous organic micropollutants from water, even at very low concentrations (ppm), based exclusively on coordination chemistry at the external surface of the MOP. Specifically, we exploit the exohedral coordination positions of RhII‐MOP to coordinatively sequester pollutants bearing N‐donor atoms in aqueous solution, and then harness their exposed surface carboxyl groups to control their aqueous solubility through acid/base reactions. We validated this approach for removal of benzotriazole, benzothiazole, isoquinoline, and 1‐napthylamine from water. [ABSTRACT FROM AUTHOR]

Heteronuclear long‐range scalar coupling constants (nJCH) are a valuable tool for solving problems in organic chemistry and are especially suited for stereochemical and configurational analyses of small molecules and natural products. This tutorial will focus on the step‐by‐step implementation of several 2D 1H frequency selective HSQMBC experiments for the easy and accurate measurement of either the magnitude or both the magnitude and the sign of long‐range nJCH couplings. The performance of these experiments will be showcased with several scenarios in a range of different experimental conditions. [ABSTRACT FROM AUTHOR]

Background: The availability of soil phosphorus (P) often limits the productivities of wet tropical lowland forests. Little is known, however, about the metabolomic profile of different chemical P compounds with potentially different uses and about the cycling of P and their variability across space under different tree species in highly diverse tropical rainforests. Results: We hypothesised that the different strategies of the competing tree species to retranslocate, mineralise, mobilise, and take up P from the soil would promote distinct soil 31P profiles. We tested this hypothesis by performing a metabolomic analysis of the soils in two rainforests in French Guiana using 31P nuclear magnetic resonance (NMR). We analysed 31P NMR chemical shifts in soil solutions of model P compounds, including inorganic phosphates, orthophosphate mono- and diesters, phosphonates, and organic polyphosphates. The identity of the tree species (growing above the soil samples) explained > 53% of the total variance of the 31P NMR metabolomic profiles of the soils, suggesting species-specific ecological niches and/or species-specific interactions with the soil microbiome and soil trophic web structure and functionality determining the use and production of P compounds. Differences at regional and topographic levels also explained some part of the the total variance of the 31P NMR profiles, although less than the influence of the tree species. Multivariate analyses of soil 31P NMR metabolomics data indicated higher soil concentrations of P biomolecules involved in the active use of P (nucleic acids and molecules involved with energy and anabolism) in soils with lower concentrations of total soil P and higher concentrations of P-storing biomolecules in soils with higher concentrations of total P. Conclusions: The results strongly suggest "niches" of soil P profiles associated with physical gradients, mostly topographic position, and with the specific distribution of species along this gradient, which is associated with species-specific strategies of soil P mineralisation, mobilisation, use, and uptake. [ABSTRACT FROM AUTHOR]

Combining an electrophilic iron complex [Fe(Fpda)(THF)]2 (3) [Fpda=N,N′‐bis(pentafluorophenyl)‐o‐phenylenediamide] with the pre‐activation of α‐alkyl‐substituted α‐diazoesters reagents by LiAl(ORF)4 [ORF=(OC(CF3)3] provides unprecedented access to selective iron‐catalyzed intramolecular functionalization of strong alkyl C(sp3)−H bonds. Reactions occur at 25 °C via α‐alkyl‐metallocarbene intermediates, and with activity/selectivity levels similar to those of rhodium carboxylate catalysts. Mechanistic investigations reveal a crucial role of the lithium cation in the rate‐determining formation of the electrophilic iron‐carbene intermediate, which then proceeds by concerted insertion into the C−H bond. [ABSTRACT FROM AUTHOR]

Combining an electrophilic iron complex [Fe(Fpda)(THF)]2 (3) [Fpda=N,N′‐bis(pentafluorophenyl)‐o‐phenylenediamide] with the pre‐activation of α‐alkyl‐substituted α‐diazoesters reagents by LiAl(ORF)4 [ORF=(OC(CF3)3] provides unprecedented access to selective iron‐catalyzed intramolecular functionalization of strong alkyl C(sp3)−H bonds. Reactions occur at 25 °C via α‐alkyl‐metallocarbene intermediates, and with activity/selectivity levels similar to those of rhodium carboxylate catalysts. Mechanistic investigations reveal a crucial role of the lithium cation in the rate‐determining formation of the electrophilic iron‐carbene intermediate, which then proceeds by concerted insertion into the C−H bond. [ABSTRACT FROM AUTHOR]

Commonly used DFT methods for the calculation of 1JCH coupling constants have typically required the application of ad hoc correction factors, modification of functionals, or empirical scaling to improve the fit between predicted and experimental values. Here we demonstrate that highly accurate 1JCH coupling predictions can be obtained without such adjustments by careful selection of DFT methods for geometry optimization and J-coupling calculations (e.g. B3LYP/6-31G(d,p)(mixed)//mPW1PW/cc-pVTZ). The proposed method was cross-validated against a diverse set of 122 1JCH couplings and was successfully applied to the conformational and stereochemical analysis of strychnine and a previously unreported trachylobane diterpene natural product. [ABSTRACT FROM AUTHOR]

The article presents chemical equations related to the article "Enantioselective Rhodium(I) Donor Carbenoid-Mediated Cascade Triggered by a Base-Free Decomposition of Arylsulfonyl Hydrazones" by Oscar Torres published in the " Chemistry: A European Journal" in 2015.

Review: 155 refs. [ABSTRACT FROM AUTHOR]

In recent years, a great interest in the development of new broadband 1H homonuclear decoupled techniques providing simplified JHH multiplet patterns has emerged again in the field of small molecule NMR. The resulting highly*‐resolved 1H NMR spectra display resonances as collapsed singlets, therefore minimizing signal overlap and expediting spectral analysis. Dr. Teodor Parella and Laura Castañar present a comprehensive compilation of the most recent advances in pure shift NMR spectroscopy, with a detailed discussion about the most relevant practical aspects in terms of pulse sequence design, selectivity, sensitivity, spectral resolution and performance. The implementation of the different reported strategies into traditional 1D and 2D NMR experiments is described and the combination with other complementary resolution‐enhanced NMR techniques opens the door of the revolutionary concept of ultra high‐resolved NMR spectroscopy. The usefulness of these novel techniques are illustrated for a number of challenging practical applications, such as the determination/ differentiation of very small chemical shift differences, analysis of highly crowded spectral regions, and the simplified and precise determination of relevant NMR parameters such as coupling constants, relaxation times or diffusion coefficients. [ABSTRACT FROM AUTHOR]

1,n‐ADEQUATE is a powerful NMR technique for elucidating the structure of proton‐deficient small molecules that can help establish the carbon skeleton of a given molecule by providing long‐range three‐bond 13C─13C correlations. Care must be taken when using the experiment to identify the simultaneous presence of one‐bond 13C─13C correlations that are not filtered out, unlike the HMBC experiment that has a low‐pass J‐filter to filter 1JCH responses out. Dual‐optimized, inverted 1JCC 1,n‐ADEQUATE is an improved variant of the experiment that affords broadband inversion of direct responses, obviating the need to take additional steps to identify these correlations. Even though ADEQUATE experiments can now be acquired in a reasonable amount of experimental time if a cryogenic probe is available, low sensitivity is still the main impediment limiting the application of this elegant experiment. Here, we wish to report a further refinement that incorporates real‐time bilinear rotation decoupling‐based homodecoupling methodology into the dual‐optimized, inverted 1JCC 1,n‐ADEQUATE pulse sequence. Improved sensitivity and resolution are achieved by collapsing homonuclear proton–proton couplings from the observed multiplets for most spin systems. The application of the method is illustrated with several model compounds. [ABSTRACT FROM AUTHOR]

The surface chemistry of Metal–Organic Polyhedra (MOPs) is crucial to their physicochemical properties because it governs how they interact with external substances such as solvents, synthetic organic molecules, metal ions, and even biomolecules. Consequently, the advancement of synthetic methods that facilitate the incorporation of diverse functional groups onto MOP surfaces will significantly broaden the range of properties and potential applications for MOPs. This study describes the use of copper(I)‐catalysed, azide–alkyne cycloaddition (CuAAC) click reactions to post‐synthetically modify the surface of alkyne‐functionalised cuboctahedral MOPs. To this end, a novel Rh(II)‐based MOP with 24 available surface alkyne groups was synthesised. Each of the 24 alkyne groups on the surface of the "clickable" Rh‐MOP can react with azide‐containing molecules at room temperature, without compromising the integrity of the MOP. The wide substrate catalogue and orthogonal nature of CuAAC click chemistry was exploited to densely functionalise MOPs with diverse functional groups, including polymers, carboxylic and phosphonic acids, and even biotin moieties, which retained their recognition capabilities once anchored onto the surface of the MOP. [ABSTRACT FROM AUTHOR]

The addition of two unsymmetric malonate esters to the Buckminster fullerene C60 can lead to 22 spectroscopically distinguishable isomeric products and therefore represents a formidable synthesis challenge. In this work, we achieve 87 % selectivity for the formation of a single (in,out‐trans‐3) isomer by combining three approaches: (i) we use a starting material, in which the two malonates are covalently connected (tether approach); (ii) we form the strong supramolecular complex of C60 with the shape‐persistent [10]CPP macrocycle (template approach) and (iii) we embed this complex further within a self‐assembled nanocapsule (shadow mask approach). Variation of the spacer chain shed light on the limitations of the approach and the ring dynamics in the unusual [2]catenanes were studied in silico with atomistic resolution. This work significantly widens the scope of mechanically interlocked architectures comprising cycloparaphenylenes (CPP). [ABSTRACT FROM AUTHOR]

Die Addition von zwei unsymmetrischen Malonsäureestern an das Buckminster‐Fulleren C60 kann zu 22 spektroskopisch unterscheidbaren isomeren Produkten führen und stellt daher eine beachtliche synthetische Herausforderung dar. In dieser Arbeit erreichen wir eine Selektivität von 87 % für die Bildung eines einzigen (in,out‐trans‐3)‐Isomers, indem wir drei Methoden kombinieren: (i) wir verwenden ein Ausgangsmaterial, in dem die beiden Malonsäureester kovalent verbunden sind (Tether); (ii) wir bilden den starken supramolekularen Komplex von C60 mit dem formstabilen [10]CPP‐Makrozyklus (Nanohoop‐Template) und (iii) wir schlossen diesen Komplex weiter in eine selbstorganisierte Nanokapsel ein (Schattenmaske). Die Variation der Alkylkette zeigte die Limitationen der Methode auf und die Ringdynamik in den ungewöhnlichen [2]Catenanen wurde in silico mit atomistischer Auflösung untersucht. Diese Arbeit erweitert das Spektrum der mechanisch ineinandergreifenden Architekturen mit Cycloparaphenylen (CPP) erheblich. [ABSTRACT FROM AUTHOR]

A number of J -upscaled NMR experiments are currently available to measure coupling constants along the indirect F1 dimension of a 2D spectrum. A major drawback is the limited F1 digital resolution that requires long acquisition times in order to achieve reasonably accurate measures. Here is shown how high levels of F1 digital resolution in a multiple-purpose HSQC experiment can be easily achieved by implementing a general J /δ-scaling strategy. In particular, a set of new J -resolved HSQC experiments is presented for a faster and much more accurate J determination in small molecules. Several options and practical aspects are discussed and exemplified by measuring the magnitude and/or the sign of several homo- and heteronuclear coupling constants in one shot. [ABSTRACT FROM AUTHOR]

A fast residual dipolar coupling constant-assisted strategy involving the simultaneous determination of scalar and total coupling constants from a single 1 JCH/2 JHH-resolved NMR spectrum is reported. It is shown that the concerted use of the directly measured 1 DCH (for all CHn multiplicities) and 2 DHH residual dipolar couplings allows an on-the-fly assignment of diastereotopic CH2 protons, as well as of an efficient discrimination between diastereoisomeric structures of strychnine which contains six stereocenters. Copyright © 2017 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Selective refocusing (GSERF or the recent PSYCHEDELIC) experiments were originally designed to determine all proton-proton coupling constants ( JHH) for a selected proton resonance. They work for isolated signals on which selective excitation can be successfully applied but, as it happens in other selective experiments, fail for overlapped signals. To circumvent this limitation, a doubly-selective TOCSY-GSERF scheme is presented for the measurement of JHH in protons resonating in crowded regions. This new experiment takes advantage of the editing features of an initial TOCSY transfer to uncover hidden resonances that become accessible to perform the subsequent frequency-selective refocusing. Copyright © 2016 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Review: 28 refs. [ABSTRACT FROM AUTHOR]

A rhodium-catalyzed asymmetric synthesis of 5,5-disubstituted cyclohexa-1,3-dienes has been achieved by [2+2+2] cycloaddition reactions between diynes and Morita-Baylis-Hillman (M-B-H) adducts as unsaturated substrates. Products containing two adjacent chiral centres (quaternary and tertiary, respectively) were obtained with complete diastereoselectivity and high enantioselectivity (84-97%) through a kinetic resolution of the M-B-H adduct. Furthermore, these highly substituted cyclohexadienes reacted with dienophiles to afford the corresponding Diels-Alder cycloadducts in good yields. [ABSTRACT FROM AUTHOR]

A revised structure for the Lycopodium alkaloid huperzine N is proposed and confirmed by synthesis. The key synthetic steps involve an epimerization of a cis-5-oxodecahydroquinoline to the corresponding trans isomer and a coupling, followed by a diastereoselective hydrogenation using Wilkinson's catalyst to incorporate the pyridylmethyl moiety. This route allowed the alkaloid serralongamine A to be synthesized for the first time, and two additional steps led to the revised structure of huperzine N, both products bearing an unusual decahydroquinoline stereostructure. [ABSTRACT FROM AUTHOR]

The photoactivated evolution of a series of enantiomerically pure 5-oxymethyl-2(5H)-furanones has been investigated. The observed intramolecular photoreactions have proven to be a straightforward entry to diverse and stereochemically rich fragment-molecules, most of which contain the privileged tetrahydropyran (THP) scaffold. The formation of the THP involves a 1,5-hydrogen atom transfer process, leading to a diradical intermediate that recombines to form a new σ C–C bond. These reactions take place under both sensitized and nonsensitized conditions, and they are highly stereoselective. When the substrate contains an allyl residue, the intramolecular [2 + 2] cycloaddition leading to cyclobutanes competes advantageously. When the substrate contains a THP residue, the cyclization involves the concomitant formation of [6,6]-spiroketals with nonanomeric relationships. [ABSTRACT FROM AUTHOR]

The preparation of multifunctional chiral molecules can be greatly simplified by adopting a route via the sequential catalytic assembly of achiral building blocks. The catalytic aldol assembly of prebiotic compounds into stereodefined pentoses and hexoses is an as yet unmet challenge. Such a process would be of remarkable synthetic utility and highly significant with regard to the origin of life. Pursuing an expedient enzymatic approach, here we use engineered D-fructose-6-phosphate aldolase from Escherichia coli to prepare a series of three- to six-carbon aldoses by sequential one-pot additions of glycolaldehyde. Notably, the pertinent selection of the aldolase variant provides control of the sugar size. The stereochemical outcome of the addition was also altered to allow the synthesis of L-glucose and related derivatives. Such engineered biocatalysts may offer new routes for the straightforward synthesis of natural molecules and their analogues that circumvent the intricate enzymatic pathways forged by evolution. [ABSTRACT FROM AUTHOR]

The presence of a highly abundant passive nucleus (Z = 19 F or 31P) allows the simultaneous determination of the magnitude and the sign of up to three different heteronuclear coupling constants from each individual cross-peak observed in a 2D 1H-X selHSQMBC spectrum. Whereas J(HZ) and J(XZ) coupling constants are measured from E.COSY multiplet patterns, J(XH) is independently extracted from the complementary IPAP pattern generated along the detected F2 dimension. The incorporation of an extended TOCSY transfer allows the extraction of a complete set of all these heteronuclear coupling constants and their signs for an entire 1H subspin system. 1H-X/1H-Y time-shared versions are also proposed for the simultaneous measurement of five different couplings ( J(XH), J(YH), J(XZ), J(YZ), and J(ZH)) for multiple signals in a single NMR experiment. Copyright © 2015 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

A rapid NMR data acquisition strategy in terms of enhanced resolution per time unit for the simple and efficient determination of multiple coupling constants is described. The use of 13C spectral aliasing combined by broadband 1H homodecoupling allows accurate measurements from ultra high resolved 2D HSQC cross-peaks. [ABSTRACT FROM AUTHOR]

New Ru complexes containing the bpea-pyr ligand (bpea-pyr stands for N,N-bis(pyridin-2-ylmethyl)-3-(1H-pyrrol-1-yl)propan-1-amine), with the formula [RuCl2(bpea-pyr)(dmso)] (isomeric complexes 2a and 2b) or [Ru(CN-Me)(bpea-pyr)X)]n+ (CN-Me = 3-methyl-1-(pyridin-2-yl)-1H-imidazol-3-ium-2-ide; X = Cl, 3, or X = H2O, 4), have been prepared and fully characterized. Complexes 3 and 4 have been anchored onto an electrode surface through electropolymerization of the attached pyrrole group, yielding stable polypyrrole films. The electrochemical behaviour of 4, which displays a bielectronic Ru(IV/II) redox pair in solution, is dramatically affected by the electropolymerization process leading to the occurrence of two monoelectronic Ru(IV/III) and Ru(III/II) redox pairs in the heterogeneous system. A carbon felt modified electrode containing complex 4 (C-felt/poly-4) has been evaluated as a heterogeneous catalyst in the epoxidation of various olefin substrates using PhI(OAc)2 as an oxidant, displaying TON values of several thousands in all cases and good selectivity for the epoxide product. [ABSTRACT FROM AUTHOR]

A straightforward chemoenzymatic synthesis of four uncovered casuarine stereoisomers is described. The strategy consists of L-fuculose-1-phosphate aldolase F131A-variant-catalyzed aldol addition of dihydroxyacetone phosphate to aldehyde derivatives of 1,4-dideoxy-1,4-imino-D-arabinitol (DAB) and its enantiomer (LAB) and subsequent one-pot catalytic deprotection-reductive amination. DAB and LAB were obtained from dihydroxyacetone and aminoethanol using D-fructose-6-phosphate aldolase and L-rhamnulose-1-phosphate aldolase catalysts, respectively. The new ent-3-epi-casuarine is a strong inhibitor of α-D-glucosidase from rice and of rat intestinal sucrase. [ABSTRACT FROM AUTHOR]

Allene-ene-allene ( 2 and 5) and allene-yne-allene ( 3 and 7) N-tosyl and O-linked substrates were satisfactorily synthesised. The [2+2+2] cycloaddition reaction catalysed by the Wilkinson catalyst [RhCl(PPh3)3] was evaluated. Substrates 2 and 5, which bear a double bond in the central position, gave a tricyclic structure in a reaction in which four contiguous stereogenic centres were formed as a single diastereomer. The reaction of substrates 3 and 7, which bear a triple bond in the central position, gave a tricyclic structure with a cyclohexenic ring core, again in a diastereoselective manner. All cycloadducts were formed by a regioselective reaction of the inner allene double bond and, therefore, feature an exocyclic diene motif. A Diels-Alder reaction on N-tosyl linked cycloadducts 8 and 10 allowed pentacyclic scaffolds to be diastereoselectively constructed. The reactivity of the allenes on [2+2+2] cycloaddition reactions was studied for the first time by density functional theory calculations. This mechanistic study rationalizes the order in which the unsaturations take part in the catalytic cycle, the reactivity of the two double bonds of the allene towards the [2+2+2] cycloaddition reaction, and the diastereoselectivity of the reaction. [ABSTRACT FROM AUTHOR]

Serum 1H NMR metabolomics has been used as a diagnostic tool for screening type 2 diabetes (T2D) with chronic kidney disease (CKD) as comorbidity. This work aimed to evaluate 1H NMR data to detect the initial kidney damage and CKD in T2D subjects, through multivariate statistical analysis. Clinical data and biochemical parameters were obtained for classifying five experimental groups using KDIGO guidelines: Control (healthy subjects), T2D, T2D-CKD-mild, T2D-CKD-moderate, and T2D-CKD-severe. Serum 1H NMR spectra were recorded to follow two strategies: one based on metabolite-to-creatinine (Met/Cr) ratios as targeted metabolomics, and the second one based on untargeted metabolomics from the 1H NMR profile. A prospective biomarkers panel of the early stage of T2D-CKD based in metabolite-to-creatinine ratio (ornithine/Cr, serine/Cr, mannose/Cr, acetate/Cr, acetoacetate/Cr, formate/Cr, and glutamate/Cr) was proposed. Later, a statistical model based on non-targeted metabolomics was used to predict initial CKD, and its metabolic pathway analysis allowed identifying the most affected pathways: phenylalanine, tyrosine, and tryptophan biosynthesis; valine, leucine, and isoleucine degradation; glyoxylate and dicarboxylate metabolism; glycine, serine, and threonine metabolism; and histidine metabolism. Nonetheless, further studies with a larger cohort are advised to precise ranges in metabolite-to-creatinine ratios and evaluate the prediction pertinency to detect initial CKD in T2D patients in both statistical models proposed. [Display omitted] • Serum 1H NMR metabolomics signature to identify initial kidney damage of T2D. • Targeted PLS-DA revealed seven metabolite-to-creatinine ratios as early biomarkers. • A T2D-CKD model based on non-targeted metabolomics to predict the early stage. • Differential metabolites depicted the metabolic pathway imbalance of T2D-CKD. [ABSTRACT FROM AUTHOR]

The utility of 13C NMR spectroscopy for the differentiation of enantiomers using chiral solvating agents (CSA) is stated. Three examples involving the enantiodifferentiation of a drug, a metabolite and a reactant in aqueous and organic solutions have been chosen to show it. The intrinsic high dispersion of 13C nucleus, as well as the singlet nature of the signals in standard experiments makes 13C NMR experiments a powerful alternative or complement to 1H NMR experiments; specially, when studying pure compounds with complex proton spectra or mixtures of compounds, as in chiral metabonomics, where severe overlapping exists in proton spectrum. To evaluate and compare the quality of the enantioresolution of a NMR signal we introduce the enantiodifferentiation quotient, E, that considers the complexity of 1H multiplets (and in general the width) of the original signal. It has been observed that the error in the measurement of the enantiomeric molar ratio can be related to the E value. The sensitivity and experimental time of a wide range of chiral analyte concentrations were also assessed. [ABSTRACT FROM AUTHOR]