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Helicobacter pyloriinfection leads to a broad spectrum of disease manifestations such as gastritis, ulcer disease, and even gastric carcinoma. The genetically determined immune response and subsequent inflammation influence the degree of mucosal damage. Adhesion molecules of the CD11 cluster play an important role in adherence of neutrophils to endothelial cells in inflammation. We conducted a haplotype-based analysis of the CD11 cluster in a sample of 315 patients withH. pyloriinfection and investigated associations with gastric erosions and ulcer disease. Twelve single nucleotide polymorphisms (SNPs) covering the genesCD11a,CD11b, andCD11cwere genotyped by Taqman technology. Linkage disequilibrium (LD) was assessed within the CD11 cluster and haplotype case-control analysis was conducted. Sliding window haplotype analysis identified a haplotype consisting of the markers CD11c exon 15 and intron 31 associated with gastric ulcer disease. Patients carrying the haplotype GA bear a 2.4-fold increased risk. No significant associations of single markers with disease outcome were found. High-density LD mapping and mutation detection of CD11c in larger samples will be necessary to confirm our findings and identify the causative variant. Thus, we conclude that genetic variants in the CD11 cluster may play a role in the development of gastric ulcer in chronicH. pyloriinfection presumably by influencing leukocyte adhesion. The biological effect of genetic variants of CD11c in gastric inflammation needs further clarification. [ABSTRACT FROM AUTHOR]

Diarylmethanes play, in part, a pivotal role in the design of highly potent, chiral, nonracemic drugs whose bioactivity is typically affected by the substitution pattern of their arene units. In this context, certain arenes such as para -substituted benzenes or unsubstituted heteroarenes cause particular synthetic challenges, since such isosteric residues at the central methane carbon atom are typically indistinguishable for a chiral catalyst. Hence, the stereoselective incorporation of isosteric (hetero)arenes into chiral methane scaffolds requires the use of stoichiometrically differentiated building blocks, which is typically realized through preceding redox-modifying operations such as metalation or halogenation and thus associated with disadvantageous step- and redox-economic traits. As a counter-design, we report herein a generalized enantioselective synthesis of chiral diarylmethanes by means of an asymmetric migratory Tsuji-Wacker oxidation of simple stilbenes. The title protocol relies on the well-adjusted interplay of aerobic photoredox and selenium-π-acid catalysis to allow for the installation of a broad variety of arenes, including isosteric ones, into the methane core. Facial differentiation and regioselectivity are solely controlled by the selenium catalyst, which (a) renders the E / Z -configuration of the stilbene substrates inconsequential and (b) permits the stereodivergent synthesis of both product enantiomers from a single catalyst enantiomer, simply by employing constitutionally isomeric starting materials. Altogether, this multicatalytic platform offers the target structures with high levels of enantioselectivity in up to 97% ee , which has also been successfully exploited in expedited syntheses of antihistaminic ( R )- and ( S )-neobenodine.

We disclose a mediated electrochemical [2+2+2] annulation of alkynes with nitriles, forming substituted pyridines in a single step from low-cost, readily available starting materials. The combination of electrochemistry and a triarylamine redox mediator obviates the requirements of transition metals and additional oxidants. Besides the formation of diarylpyridine moieties via the homocoupling of two identical alkynes, the heterocoupling of two different alkynes depending on their electronic nature is possible, highlighting the unprecedented control of chemoselectivity in this catalytic [2+2+2] process. Mechanistic investigations like cyclic voltammetry and crossover experiments combined with DFT calculations indicate the initial oxidation of an alkyne as the key step leading to the formation of a vinyl radical cation intermediate. The utilization of continuous flow technology proved instrumental for an efficient process scale-up. The utility of the products is exemplified by the synthesis of π-extended molecules, being relevant for material or drug synthesis., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The unimolecular heterolysis of covalent σ-bonds is integral to many chemical transformations, including S N 1-, E1- and 1,2-migration reactions. To a first approximation, the unequal redistribution of electron density during bond heterolysis is governed by the difference in polarity of the two departing bonding partners 1-3 . This means that if a σ-bond consists of two identical groups (that is, symmetric σ-bonds), its unimolecular fission from the S 0 , S 1 , or T 1 states only occurs homolytically after thermal or photochemical activation 1-7 . To force symmetric σ-bonds into heterolytic manifolds, co-activation by bimolecular noncovalent interactions is necessary 4 . These tactics are only applicable to σ-bond constituents susceptible to such polarizing effects, and often suffer from inefficient chemoselectivity in polyfunctional molecules. Here we report the net heterolysis of symmetric and homopolar σ-bonds (that is, those with similar electronegativity and equal leaving group ability 3 ) by means of stimulated doublet-doublet electron transfer (SDET). As exemplified by Se-Se and C-Se σ-bonds, symmetric and homopolar bonds initially undergo thermal homolysis, followed by photochemically SDET, eventually leading to net heterolysis. Two key factors make this process feasible and synthetically valuable: (1) photoexcitation probably occurs in only one of the incipient radical pair members, thus leading to coincidental symmetry breaking 8 and consequently net heterolysis even of symmetric σ-bonds. (2) If non-identical radicals are formed, each radical may be excited at different wavelengths, thus rendering the net heterolysis highly chemospecific and orthogonal to conventional heterolyses. This feature is demonstrated in a series of atypical S N 1 reactions, in which selenides show SDET-induced nucleofugalities 3 rivalling those of more electronegative halides or diazoniums., (© 2024. The Author(s).)

Photocatalytic reactions involving a reductive radical-polar crossover (RRPCO) generate intermediates with carbanionic reactivity. Many of these proposed intermediates resemble highly reactive organometallic compounds. However, conditions of their formation are generally not tolerated by their isolated organometallic versions and often a different reactivity is observed. Our investigations on their nature and reactivity under commonly used photocatalytic conditions demonstrate that these intermediates are indeed best described as free, superbasic carbanions capable of deprotonating common polar solvents usually assumed to be inert such as acetonitrile, dimethylformamide, and dimethylsulfoxide. Their basicity not only towards solvents but also towards electrophiles, such as aldehydes, ketones, and esters, is comparable to the reactivity of isolated carbanions in the gas-phase. Previously unsuccessful transformations thought to result from a lack of reactivity are explained by their high reactivity towards the solvent and weakly acidic protons of reaction partners. An intuitive explanation for the mode of action of photocatalytically generated carbanions is provided, which enables methods to verify reaction mechanisms proposed to involve an RRPCO step and to identify the reasons for the limitations of current methods., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

We show that countercations exert a remarkable influence on the ability of anionic cobaltate salts to catalyze challenging alkene hydrogenations. An evaluation of the catalytic properties of [Cat][Co(η 4 -cod) 2 ] (Cat=K (1), Na (2), Li (3), ( Dep nacnac)Mg (4), and N( n Bu) 4 (5); cod=1,5-cyclooctadiene, Dep nacnac={2,6-Et 2 C 6 H 3 NC(CH 3 )} 2 CH)]) demonstrated that the lithium salt 3 and magnesium salt 4 drastically outperform the other catalysts. Complex 4 was the most active catalyst, which readily promotes the hydrogenation of highly congested alkenes under mild conditions. A plausible catalytic mechanism is proposed based on density functional theory (DFT) investigations. Furthermore, combined molecular dynamics (MD) simulation and DFT studies were used to examine the turnover-limiting migratory insertion step. The results of these studies suggest an active co-catalytic role of the counterion in the hydrogenation reaction through the coordination to cobalt hydride intermediates., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

We report the visible light-mediated copper-catalyzed vicinal difunctionalization of olefins utilizing bromonitroalkanes as ATRA reagents. This protocol is characterized by high yields and fast reaction times under environmentally benign reaction conditions with exceptional scope, allowing the rapid functionalization of both activated and unactivated olefins. Moreover, late-stage functionnalization of biologically active molecules and upscaling to gram quantities is demonstrated, which offers manifold possibilities for further transformations, e.g. access to nitro- and aminocyclopropanes. Besides the synthetic utility of the title transformation, this study undergirds the exclusive role of copper in photoredox catalysis showing its ability to stabilize and interact with radical intermediates in its coordination sphere. EPR studies suggest that such interactions can even outperform a highly favorable cyclization of transient to persistent radicals contrasting iridium-based photocatalysts., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Due to their high stability towards enzymatic hydrolysis C-acyl glycosidic compounds are useful synthetic intermediates for potential candidates in drug discovery. Syntheses for C-acyl mannosides have remained scarce and usually employ donors obtained from lengthy syntheses. Furthermore, syntheses of unprotected C-acyl mannosides have not been reported so far, due to the incapability of the C-acyl mannoside motif with deprotection conditions for protective groups commonly used in carbohydrate chemistry. Herein, we report an efficient and highly α-selective four-step one-pot method for the synthesis of C-acyl α-d-manno-, l-rhamno- and d-lyxopyranosides from easily accessible persilylated monosaccharides and dithianes requiring only trace amounts of a copper source as catalyst and explain the crucial role of the catalyst by mechanistic studies. Furthermore, the C-acyl α-glycosides were easily isomerized to give rapid access to their β-anomers., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Chemical bond activations mediated by H-bond interactions involving highly electronegative elements such as nitrogen and oxygen are powerful tactics in modern catalysis research. On the contrary, kindred catalytic regimes in which heavier, less electronegative elements such as selenium engage in H-bond interactions to co-activate C-Se σ-bonds under oxidative conditions are elusive. Traditional strategies to enhance the nucleofugality of selenium residues predicate on the oxidative addition of electrophiles onto Se II -centers, which entails the elimination of the resulting Se IV moieties. Catalytic procedures in which Se IV nucleofuges are substituted rather than eliminated are very rare and, so far, not applicable to carbon-carbon bond formations. In this study, we introduce an unprecedented combination of O-H⋅⋅⋅Se H-bond interactions and single electron oxidation to catalytically generate Se III nucleofuges that allow for the formation of new C-C σ-bonds by means of a type I semipinacol process in high yields and excellent selectivity., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Showcasing the concept of light-induced homolysis for the generation of radicals, the Cu II -photocatalyzed decarboxylative oxygenation of carboxylic acids with molecular oxygen as the terminal oxidant is described. Two Cu II -carboxylate complexes with different coordination geometries were synthesized and characterized by X-ray analysis, correlating their structure with their ability to initiate light-induced decarboxylations.

A stereoselective, scalable, and metal-free ring-expansion of monocyclopropanated pyrroles and furans has been developed, leading to value-added highly functionalized tetrahydropyridine and dihydro-2 H -pyran derivatives. Featuring a cyclopropylcarbinyl cation rearrangement as the key step, the selective cleavage of the unactivated endocyclic cyclopropane C-C bond is achieved. Targeted transformations of the thus obtained six-membered heterocycles give access to versatile building blocks with relevance for drug synthesis., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Biomass-derived 5-chloromethylfurfural (CMF), a congener of the well-known carbohydrate-based platform chemical 5-hydroxymethylfurfural (HMF), can efficiently be functionalised by radical transformations of its benzylic chloromethyl group. We report here the first examples of these radical reactions by way of metal-free, triethylborane/oxygen-induced atom transfer radical addition (ATRA) reactions between CMF and styrenes, which proceed with high yield and selectivity. The key intermediate, the 2-formyl-5-furfuryl radical derived from CMF, and its radical addition reactions were studied with regard to its electronic structure, i.e. spin density distribution and frontier molecular orbitals based on the NBO ansatz and activation barriers of the addition step using DFT and post-HF methods.

Reversing the regioselectivity of the renowned Diels-Alder reaction by overriding the usual thermodynamic and kinetic governing factors has always been a formidable challenge to synthetic organic chemists. Anthracenes are well-known to undergo [4 + 2]-cycloadditions with dienophiles at their 9,10-positions (central ring) over 1,4-positions (terminal ring) guided by the relative aromatic stabilization energy of the two possible products, and also by harboring the largest orbital coefficients of the highest occupied molecular orbital (HOMO) at the 9,10-positions. We, herein, report a 1,4-selective [4 + 2]-cycloaddition strategy of 9,10-unsubstituted anthracenes by installing electron-donating substituents on the terminal rings which is heretofore unprecedented to the best of our knowledge. The developed synthetic strategy does not require any premeditated engagement of the 9,10-positions either with any sterically bulky or electron-withdrawing substituents and allows delicate calibration of the regioselectivity by modulating the electron-donating strength of the substituents on the terminal rings. Likewise, the regioselective functionalization of the terminal anthracene ring in electrophilic substitution reactions is demonstrated. A mechanistic rationale is offered with the aid of detailed computational studies, and finally, synthetic applications are presented., (© 2020. The Author(s).)

We report a new synthetic route to a series of α-carboxynitrobenzyl photocaged l-aspartates for application in time-resolved structural biology. The resulting compounds were characterised in terms of UV/Vis absorption properties, aqueous solubility and stability, and photocleavage rates ( τ = μs to ms) and quantum yields ( φ = 0.05 to 0.14)., Competing Interests: The authors declare no conflicts of interest., (This journal is © The Royal Society of Chemistry.)

Objective: To study patient and provider feedback on how a multimedia platform (EngagedMD) helps patients to understand the risks and consequences of in vitro fertilization (IVF), ovulation induction (OI), and intrauterine insemination (IUI) treatments and the impact of the informed consent process., Design: Prospective survey study., Setting: IVF units in the United States., Patient(s): Six-thousand three-hundred and thirty-three patients who viewed the multimedia platform before IVF or OI-IUI treatment at 13 U.S. IVF centers and 128 providers., Intervention(s): Quantitative survey with 17 questions., Main Outcome Measure(s): Assessment of the impact of a multimedia platform on patient anxiety, comprehension, and satisfaction and provider/nurse feedback related to the informed consent process., Result(s): The survey was completed by 3,097 respondents (66% IVF treatment; 34% OI-IUI treatment) and 44 providers. Overall, 93% felt the media platform was intuitive, and 90% and 95% felt it had appropriate duration and detail, respectively. Most agreed/strongly agreed it better prepared them to consent (88%), increased their comfort in pursuing treatment (77%) and increased their satisfaction with their care (83%). Compared with the OI-IUI group, statistically significantly more participants who viewed the IVF media platform strongly agreed that the comprehension questions reinforced key concepts (47% vs. 40%), educated them about treatment risks (55% vs. 44%), helped them ask providers informed questions (45% vs. 36%), and better prepared them to sign consent forms (46% vs. 37%). Overall, 63% of providers felt that the media platform improved patient learning, made patients more accountable, and standardized information dissemination., Conclusion(s): The EngagedMD media platform improves patient knowledge, satisfaction, and control over medical decision making and better prepares patients to give informed consent. Furthermore, it is well-liked by providers and is easily implemented., (Copyright © 2018 American Society for Reproductive Medicine. Published by Elsevier Inc. All rights reserved.)

Embedded medium-sized carbacycles and cyclohepta[b]indoles occur frequently as scaffold elements in natural products and bioactive compounds. Described herein is a conceptionally novel photochemically triggered cascade process to these scaffolds. Key to the cascading ring-expansion process is an unprecedented intramolecular alkyne analogue of the de Mayo reaction., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Despite ample evidence for the unique reactivity offered by hypervalent F-iodanes, mechanistic investigations fall far behind. In order to shed light on the unusual behavior of such F-reagents, we conducted computational and experimental studies on the chemodivergent transformation of styrenes. We identified the spirocyclic F-cyclopropane as the common intermediate for both the C, H-fluorination and C, H-amination pathways. The fate of this key compound is determined by the extent of cationic charge delocalization controlled by the N-substituents. Exploiting this phenomenon, a multitude of different transformations have become available, leading, i.e., to the regiodivergent synthesis of indoles and tryptophans.

Electron-rich arenes react with aryl and alkyl disulfides in the presence of catalytic amounts of [Ir(dF(CF 3 )ppy) 2 (dtbpy)]PF 6 and (NH 4 ) 2 S 2 O 8 under blue light irradiation to yield arylthiols. The reaction proceeds at room temperature and avoids the use of prefunctionalized arenes. Experimental evidence suggests a radical-radical cross coupling mechanism.

The visible-light-mediated activation of vinyl chlorides derived from α-chloro ethyl cinnamates via oxidative quenching of excited photocatalyst fac-Ir(ppy) 3 is described. Upon photoelectron transfer and chloride extrusion, the corresponding vinyl radical can be efficiently trapped by enol acetates, giving rise to synthetically useful 1,4-dicarbonyl compounds in good to excellent yields. This transformation is distinguished by mild and environmentally benign reaction conditions and can be performed on a multigram scale, in sharp contrast to contrasting α-bromo ethyl cinnamates, which show low conversion under the various conditions applied.

The visible-light-accelerated oxo-azidation of vinyl arenes with trimethylsilylazide and molecular oxygen as stoichiometric oxidant was achieved. In contrast to photocatalysts based on iridium, ruthenium, or organic dyes, [Cu(dap) 2 ]Cl or [Cu(dap)Cl 2 ] were found to be unique for this transformation, which is attributed to their ability to interact with the substrates through ligand exchange and rebound mechanisms. Cu II is proposed as the catalytically active species, which upon coordinating azide will undergo light-accelerated homolysis to form Cu I and azide radicals. This activation principle (Cu II -X→Cu I +X . ) opens up new avenues for copper-based photocatalysis., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A stereoselective hypervalent iodine-promoted oxidative rearrangement of 1,1-disubstituted alkenes has been developed. This practically simple protocol provides access to enantioenriched α-arylated ketones without the use of transition metals from readily accessible alkenes., (© 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

The Breslow catalytic cycle describing the benzoin condensation promoted by N-heterocyclic carbenes (NHC) as proposed in the late 1950s has since then been tried by generations of physical organic chemists. Emphasis has been laid on proofing the existence of an enaminol like structure (Breslow intermediate) that explains the observed umpolung of an otherwise electrophilic aldehyde. The present study is not focusing on spectroscopic elucidation of a thiazolydene based Breslow intermediate but rather tries to clarify if this key-intermediate is indeed directly linked with the product side of the overall reaction. The here presented EPR-spectroscopic and computational data provide a fundamentally different view on how the benzoin condensation may proceed: a radical pair could be identified as a second key-intermediate that is derived from the Breslow-intermediate via an SET process. These results highlight the close relationship to the Cannizarro reaction and oxidative transformations of aldehydes under NHC catalysis.

Allylic oxidations of olefins to enones allow the efficient synthesis of value-added products from simple olefinic precursors like terpenes or terpenoids. Biocatalytic variants have a large potential for industrial applications, particularly in the pharmaceutical and food industry. Herein we report efficient biocatalytic allylic oxidations of spirocyclic terpenoids by a lyophilisate of the edible fungus Pleurotus sapidus. This ''mushroom catalysis'' is operationally simple and allows the conversion of various unsaturated spirocyclic terpenoids. A number of new spirocyclic enones have thus been obtained with good regio- and chemoselectivity and chiral separation protocols for enantiomeric mixtures have been developed. The oxidations follow a radical mechanism and the regioselectivity of the reaction is mainly determined by bond-dissociation energies of the available allylic CH-bonds and steric accessibility of the oxidation site.

Aromatic substituents migrate in a novel oxidative cyclization mediated by iodine(III) reagents. 4-Arylbut-3-enoic acids are cyclized and rearranged to 4-arylfuran-2(5H)-ones by hypervalent iodine compounds in good to excellent yields under mild reaction conditions. Other ring sizes are also accessible. The mechanism of the reaction is described in detail, and calculations highlight the cationic nature of the intermediates in the rearrangement. The fast access to heavily substituted furanones is used for the synthesis of biologically active derivatives.

Reaction rates and product selectivity of kinetically controlled reactions are not always sufficiently described by standard RRKM or TST theory. Reactions taking place on potential energy surfaces featuring a valley ridge inflection point belong to this class of reactions. Though various research groups could show that reaction path bifurcations are far from being an exception in organic reactions the underlying principles that govern product distributions of those bifurcating reaction pathways are yet not fully understood. This Perspective has the intention to provide an overview of how far our understanding and the development of the theoretical foundation have progressed.

The kinetics of the Cu(II)(bisoxazoline)-catalyzed diastereo- and enantioselective Gosteli-Claisen rearrangement of 2-alkoxycarbonyl-substituted allyl vinyl ethers has been investigated by enantioselective on-column reaction gas chromatography (ocRGC). Enantioselective ocRGC integrates (stereoselective) catalysis and enantioselective chromatography in a single microcapillary, which is installed in a GC-MS for direct analysis of conversion and selectivity. Thus, this technique allows direct differentiation of thermal and stereoselectively catalyzed reaction pathways and determination of activation parameters and selectivities of the individual reaction pathways starting from stereoisomeric reactants with high precision. Two modes of operation of enantioselective ocRGC are presented to investigate noncatalyzed, i.e., conversion of isopropyl-2-(allyloxy)but-2Z-enoate 1 to isopropyl-3R,S-methyl-2-oxy-hex-5-enoate (±)-2 and the [Cu{(R,R)-Ph-box}](SbF(6))(2)-catalyzed Gosteli-Claisen rearrangement, i.e., conversion of isopropyl-2-(but-2'E-en-1-yloxy)but-2Z-enoate (E,Z)-3 to isopropyl-3S,4S-dimethyl-2-oxy-hex-5-enoate 4b. Eyring activation parameters have been determined by temperature-dependent measurements: Uncatalyzed rearrangement of 1 to (±)-2 gives ΔG(‡) (298 K) = 114.1 ± 0.2 kJ·mol(-1), ΔH(‡) = 101.1 ± 1.9 kJ·mol(-1), and ΔS(‡) = -44 ± 5 J·(K·mol)(-1), and catalyzed rearrangement of (E,Z)-3 to 4b gives ΔG(‡)(298 K) = 101.1 ± 0.3 kJ·mol(-1), ΔH(‡) = 106.1 ± 6.6 kJ·mol(-1), and ΔS(‡) = 17 ± 19 J·(K·mol)(-1).

The ambivalent reactivity of 2-alkoxycarbonyl-substituted propargyl vinyl ethers has been explored. Depending on the conditions, the catalyzed and uncatalyzed Gosteli-Claisen rearrangement triggers downstream transformations that cascade from initially formed γ-allenyl α-keto esters to highly substituted furanes and cyclopentenes. In support of a mechanistic hypothesis, the results of a DFT study using the B1B95 and B3LYP functionals are revealed., (© 2011 American Chemical Society)

We report the details of the total synthesis of natural and non-natural jatropha-5,12-dienes. The successful tactic for the assembly of the strained trans-bicyclo[10.3.0]pentadecane scaffold employed a B-alkyl Suzuki-Miyaura cross-coupling for the formation of the C5/C6 double bond and a ring-closing metathesis for the construction of the C12/C13 double bond. The key step of the synthesis of the cyclopentane fragment, an uncatalyzed intramolecular carbonyl-ene reaction, was studied computationally by DFT calculations. The members of the ensemble of synthetic natural and non-natural jatrophanes were subsequently examined as modulators for the ABCB1, ABCG2, and ABCC1 efflux proteins, which are associated with multidrug resistance in cancer chemotherapy.

The oily product ZANTHIN consists of natural astaxanthin, which is manufactured from the microalgae Haematococcus pluvialis by supercritical CO(2) extraction. An HPLC method was developed to separate all of the components of the complex astaxanthin extract using a C(30) column. The separation resulted in different isomers of astaxanthin accompanied by two other carotenoids. The main component consisted of astaxanthin singly esterified with several different fatty acids. C18:3, C18:2, C18:1 and C16:0 were identified as the most commonly occurring fatty acids. Doubly esterified astaxanthin was also found, although in lower concentrations compared to singly esterified astaxanthin. After performing a detailed fatty acid analysis by GC-MS, the peaks from the extract were assigned via HPLC-MS. A trans to cis transmutation of the all-trans compound was performed by thermal treatment in order to obtain an enrichment of cis isomers as the basis for unambiguous identification via NMR experiments. The all-trans as well as the 9- and 13-cis isomers of astaxanthin were characterized in detail by UV/Vis, (1)H, and (1)H,(1)H COSY NMR spectroscopy.

In the title compound, [Cu(C(17)H(30)N(2)O(2))(C(3)H(7)NO)(2)][SbF(6)](2), which is a potential catalyst in the asymmetric Gosteli-Claisen rearrangement, the Cu atom adopts a distorted cis-CuN(2)O(2) square-planar geometry arising from N,N'-bidentate coordin-ation by the chiral ligand and two O-bonded dimethyl-formamide mol-ecules. Two short C-H⋯O contacts occur within the ligand and two weak inter-molecular C-H⋯F bonds may help to establish the packing.