bluuebunny/crossref_metadata_2025_split huggingface dataset:
Multimeric Cyclic RGD Peptides as Potential Tools for Tumor Targeting: Solid‐Phase Peptide Synthesis and Chemoselective Oxime Ligation
Authors: Thumshirn Georgette , Hersel Ulrich , Goodman Simon L. , Kessler Horst 
Published: May 2003

AbstractThe αvβ3 integrin receptor plays an important role in human metastasis and tumor‐induced angiogenesis. Targeting this receptor may provide information about the receptor status of the tumor and enable specific therapeutic planning. Solid‐phase peptide synthesis of multimeric cyclo(‐RGDfE‐)‐peptides is described, which offer the possibility of enhanced integrin targeting due to polyvalency effects. These peptides contain an aminooxy group for versatile chemoselective oxime ligation. Conjugation with para‐trimethylstannylbenzaldehyde results in a precursor for radioiododestannylation, which would allow them to be used as potential tools for targeting and imaging αvβ3‐expressing tumor cells. The conjugates were obtained in good yield without the need of a protection strategy and under mild conditions.
Synthesis and Characterization of Ion‐Exchangeable Titanate Nanotubes
Authors: Sun Xiaoming , Li Yadong 
Published: May 2003

AbstractTitanate nanotubes were synthesized under hydrothermal conditions. The optimized synthesis (100–180 °C, longer than 48 h), thermal and hydrothermal stability, ion exchangeability and consequent magnetic and optical properties of the titanate nanotubes were systematically studied in this paper. First, nanotubes with monodisperse pore‐size distribution were prepared. The formation mechanism of the titanate nanotubes was also studied. Second, the thermal and hydrothermal stability were characterized with Xray diffraction (XRD), high‐resolution transmission electron microscopy (HRTEM), Fourier transform infrared (FTIR), and Raman spectroscopy. Results showed that sodium ions played a significant role in the stability of the frameworks. Third, the selective ion exchangeability was demonstrated with a series of ions. The ion substitution also enlarged the BET surface area of the titanate nanotubes to 240 m2 g−1. Combination of these two features implied that these nanotubes might be functionalized by substitution of different transitional‐metal ions and consequently used for selective catalysis. Magnetism, photoluminescence, and UV/Vis spectra of the substituted titanate nanotubes revealed that the magnetic and optical properties of the nanotubes were modifiable.
Definitive Ab Initio Studies of Model SN2 Reactions CH3X+F− (X=F, Cl, CN, OH, SH, NH2, PH2)
Authors: Gonzales Jason M. , Pak Chaeho , Cox R. Sidney , Allen Wesley D. , Schaefer III Henry F. , Császár Attila G. , Tarczay György 
Published: May 2003

AbstractThe energetics of the stationary points of the gas‐phase reactions CH3X+F−→CH3F+X− (X=F, Cl, CN, OH, SH, NH2 and PH2) have been definitively computed using focal point analyses. These analyses entailed extrapolation to the one‐particle limit for the Hartree–Fock and MP2 energies using basis sets of up to aug‐cc‐pV5Z quality, inclusion of higher‐order electron correlation [CCSD and CCSD(T)] with basis sets of aug‐cc‐pVTZ quality, and addition of auxiliary terms for core correlation and scalar relativistic effects. The final net activation barriers for the forward reactions are: E$\rm{_{F,F}^{\,b}}$=−0.8, E$\rm{_{F,Cl}^{\,b}}$=−12.2, E$\rm{_{F,CN}^{\,b}}$=+13.6, E$\rm{_{F,OH}^{\,b}}$=+16.1, E$\rm{_{F,SH}^{\,b}}$=+2.8, E$\rm{_{F,NH_{2}}^{\,b}}$=+32.8, and E$\rm{_{F,PH_{2}}^{\,b}}$=+19.7 kcal mol−1. For the reverse reactions E$\rm{_{F,F}^{\,b}}$=−0.8, E$\rm{_{Cl,F}^{\,b}}$=+18.3, E$\rm{_{CN,F}^{\,b}}$=+12.2, E$\rm{_{OH,F}^{\,b}}$=−1.8, E$\rm{_{SH,F}^{\,b}}$=+13.2, E$\rm{_{NH_{2},F}^{\,b}}$=−1.5, and E$\rm{_{PH_{2},F}^{\,b}}$=+9.6 kcal mol−1. The change in energetics between the CCSD(T)/aug‐cc‐pVTZ reference prediction and the final extrapolated focal point value is generally 0.5–1.0 kcal mol−1. The inclusion of a tight d function in the basis sets for second‐row atoms, that is, utilizing the aug‐cc‐pV(X+d)Z series, appears to change the relative energies by only 0.2 kcal mol−1. Additionally, several decomposition schemes have been utilized to partition the ion–molecule complexation energies, namely the Morokuma–Kitaura (MK), reduced variational space (RVS), and symmetry adapted perturbation theory (SAPT) techniques. The reactant complexes fall into two groups, mostly electrostatic complexes (FCH3⋅F− and ClCH3⋅F−), and those with substantial covalent character (NCCH3⋅F−, CH3OH⋅F−, CH3SH⋅F−, CH3NH2⋅F− and CH3PH2⋅F−). All of the product complexes are of the form FCH3⋅X− and are primarily electrostatic.
A New Strategy for the Design of Water‐Soluble Synthetic Receptors: Specific Recognition of DNA Intercalators and Diamines.
Authors: Wada Kenji , Mizutani Tadashi , Matsuoka Hideki , Kitagawa Susumu 
Published: May 2003

AbstractWater‐soluble zinc bisporphyrin receptors 1 and 2 having two Lewis acidic sites (zinc) in the hydrophobic environment consisting of alkyl chains and a bisporphyrin framework, and covered with hydrophilic exterior (twelve or eighteen carboxyl groups) were prepared. The receptors show high affinity for diamines and DNA intercalators in water where the binding constants Ka are of the order of 107 and 108 M−1, respectively. Diamines and DNA intercalators are bound to the receptor through different mechanisms. Diamines are bound through hydrophobic interactions and zinc–nitrogen interactions, while DNA intercalators are bound through hydrophobic interactions and charge‐transfer interactions. Flexible alkyl chains can make van der Waals contact with guests and create a hydrophobic environment around the bound guest by an induced‐fit‐type mechanism. For the binding of DNA intercalators, the following features are noteworthy: 1) Binding constants are similar between the zinc porphyrins and zinc‐free porphyrins; 2) the binding constant is larger for the guest having the lower LUMO; this indicates the important contribution of charge‐transfer interactions to binding; 3) the hydrophobic and cationic nature of DNA intercalators is substantially important, and 4) higher ionic strength reduced the binding affinities; this shows a moderate contribution of electrostatic interactions. The conformational instability of the receptors also contributes to the tight binding: hydrophobic and electrostatic interactions cannot both be favorable at the same time in the guest‐free receptor. Enthalpy–entropy compensation observed for the binding of diamines and DNA intercalators is characterized by a relatively small slope (α=0.74) and a large intercept (β=7.75 kcal mol−1) in the ΔH ° versus TΔS ° plot; this shows that a conformational change of receptors and a significant desolvation occur upon binding. The receptor can competitively bind to propidium iodide to deprive DNA of the intercalated propidium iodide. These features of water‐soluble receptors consisting of a rigid framework and flexible side chains with a large solvent‐accessible area are in contrast to highly preorganized rigid receptors, and they can provide useful guidelines for rational design of induced‐fit artificial receptors in water.
Self‐Assembled Monolayers of Novel Surface‐Bound Dendrons: Peripheral Structure Determines Surface Organization
Authors: Dong Bin , Huo Fengwei , Zhang Lu , Yang Xunyu , Wang Zhiqiang , Zhang Xi , Gong Shaoyun , Li Jinghong 
Published: May 2003

AbstractThe synthetic and functional versatility of dendrimers and their well‐defined shapes make them attractive molecules for surface modification. We synthesized six structurally very similar surface‐bound dendrons and used them as building blocks for the preparation of self‐assembled monolayers (SAMs) on a gold surface. We studied the effects of the surface‐bound dendron's main structure, peripheral substituents, and the coadsorption process on its self‐assembling behavior. Using scanning tunneling microscopy (STM), we observed nanostripes for SAMs of the surface‐bound dendron consisting of symmetrical benzene rings. When we changed the symmetrical dendron's structure slightly, by increasing or decreasing the numbers of benzene rings at one wedge, we found no ordered structures were formed by the asymmetrical dendrons. We also introduced two kinds of substituents, heptane chains and oligo(ethylene oxide) chains, to the symmetrical dendron's periphery. Heptane chains appear to enhance the interaction between symmetrical backbones, leading to the formation of stripes, while oligo(ethylene oxide) chains appear to weaken the interaction between symmetrical backbones, resulting in a homogeneous structure. Dendrons with both heptane and oligo(ethylene oxide) chains exhibit nanophase separation in a confined state, leading to the formation of a honeycomb structure. Electrochemical studies provide additional evidence for understanding the resulting surface organizations: surface‐bound dendrons with symmetrical structures form denser monolayers than their asymmetrical analogues; SAMs comprising peripherally substituted dendrons exhibit blocking effects proportionate to their hydrophilic fraction.
Organic Reactions and Nanoparticle Preparation in CO2‐Induced Water/P104/p‐Xylene Microemulsions
Authors: Zhang Rui , Liu Jun , He Jun , Han Buxing , Wu Weize , Jiang Tao , Liu Zhimin , Du Jimin 
Published: May 2003

AbstractNanometer‐sized gold particles are synthesized by the reduction of HAuCl4 with KBH4 in the CO2‐induced microemulsion of (EO)27(PO)61(EO)27 (P104; EO=ethylene oxide, PO=propylene oxide)/p‐xylene/CO2/H2O. The recovery of gold particles from the microemulsion can be easily accomplished by the venting of CO2, while the surfactant remains in the organic phase. The effect of the molar ratio of the reductant to HAuCl4, the concentration of the reactants, and the molar ratio of water to EO segments (W0) in the reverse micelles on the size of the gold particles is studied. The hydrolysis of benzoyl chloride (BzCl) and p‐nitrophenyl chloroformate (NPhCl) has also been carried out in the microemulsion. The results show that the observed rate constants kobs of both substrates increase significantly with W0, and that W0 has a larger influence on the hydrolysis of BzCl. The different extents of the influence of W0 on the two reactions can be ascribed to the different reaction mechanisms and the expected changes in nucleophilicity and polarity of water in the reverse micelles.
η6‐Mesityl,η1‐Imidazolinylidene–Carbene–Ruthenium(II) Complexes: Catalytic Activity of their Allenylidene Derivatives in Alkene Metathesis and Cycloisomerisation Reactions
Authors: Çetinkaya Bekir , Demir Serpil , Özdemir Ismail , Toupet Loïc , Sémeril David , Bruneau Christian , Dixneuf Pierre H. 
Published: May 2003

AbstractThe reaction of electron‐rich carbene‐precursor olefins containing two imidazolinylidene moieties [(2,4,6‐Me3C6H2CH2)NCH2CH2N(R)C]2 (2a: R=CH2CH2OMe, 2 b R=CH2Mes), bearing at least one 2,4,6‐trimethylbenzyl (R=CH2Mes) group on the nitrogen atom, with [RuCl2(arene)]2 (arene=p‐cymene, hexamethylbenzene) selectively leads to two types of complexes. The cleavage of the chloride bridges occurs first to yield the expected (carbene) (arene)ruthenium(II) complex 3. Then a further arene displacement reaction takes place to give the chelated η6‐mesityl,η1‐carbene–ruthenium complexes 4 and 5. An analogous η6‐arene,η1‐carbene complex with a benzimidazole frame 6 was isolated from an in situ reaction between [RuCl2(p‐cymene)]2, the corresponding benzimidazolium salt and cesium carbonate. On heating, the RuCl2(imidazolinylidene) (p‐cymene) complex 8, with p‐methoxybenzyl pendent groups attached to the N atoms, leads to intramolecular p‐cymene displacement and to the chelated η6‐arene,η1‐carbene complex 9. On reaction with AgOTf and the propargylic alcohol HCCCPh2OH, compounds 4–6 were transformed into the corresponding ruthenium allenylidene intermediates (4→10, 5→11, 6→12). The in situ generated intermediates 10–12 were found to be active and selective catalysts for ring‐closing metathesis (RCM) or cycloisomerisation reactions depending on the nature of the 1,6‐dienes. Two complexes [RuCl2{η1‐CN(CH2C6H2Me3‐2,4,6)CH2CH2N‐ (CH2CH2OMe)}(C6Me6)] 3 with a monodentate carbene ligand and [RuCl2{η1‐CN[CH2(η6‐C6H2Me3‐2,4,6)]CH2CH2N‐(CH2C6H2Me3‐2,4,6)}] 5 with a chelating carbene–arene ligand were characterised by Xray crystallography.
meso‐Substituted Aromatic 34π Core‐Modified Octaphyrins: Syntheses, Characterization and Anion Binding Properties
Authors: Anand Venkataramanarao G. , Venkatraman Sundararaman , Rath Harapriya , Chandrashekar Tavarekere K. , Teng Weijie , Ruhlandt‐Senge Karin 
Published: May 2003

AbstractModified octaphyrins with 34π electrons have been synthesized and characterized following a simple synthetic methodology. An acid‐catalyzed α,α coupling of tetrapyrranes containing furan, thiophene and selenophene rings resulted in the formation of the respective octaphyrins in relatively good yield. Solution studies by 1H NMR and 2D NMR methods and single crystal Xray structural characterization reveal an almost flat structure with two heterocyclic rings inverted. Specifically, in 14 two selenophene rings (one on each biselenophene unit) are inverted while in 15 two furan rings (one on each bifuran unit) are inverted when the meso substituent are mesityl groups. On changing the mesityl substituent to m‐xylyl group as in 19, the location of ring inversion shifts to pyrrole rings (one on each bipyrrole unit) indicating the dependence of structure on the meso substituents. UV/Vis studies, both in freebase and protonated forms reveal typical porphyrinic character and the aromatic nature of the octaphyrins. The Δδ values evaluated by 1H NMR spectroscopy also support their aromatic nature. The protonated forms of octaphyrins bind TFA anion in a 1:2 ratio. The TFA anions are located one above and below the plane of the octaphyrin macrocycle and they are held by weak electrostatic NH‐O interactions similar to that observed for protonated rubyrins. However, in the present case, there is an additional non‐electrostatic CH‐O interaction involving β‐CH of the inverted heterocyclic ring and the carbonyl oxygen of the TFA. Furthermore, inter molecular interactions between the CH of the meso‐mesityl group and the fluorine of CF3 group of bound TFA leads to the formation of one‐dimensional supramolecular arrays with interplanar distance of 13 Å between two octaphyrins.
The Magnetic Properties of Myoglobin as Studied by NMR Spectroscopy
Authors: Bertini Ivano , Luchinat Claudio , Turano Paola , Battaini Giuseppe , Casella Luigi 
Published: May 2003

AbstractDeoxymyoglobin has been investigated by NMR spectroscopy to determine the magnetic anisotropy through pseudocontact shifts and the total magnetic susceptibility through Evans measurements. The magnetic anisotropy values were found to be Δχax=−2.03±0.08×10−32 m3 and Δχrh=−1.02±0.09×10−32 m3. The negative value of the axial susceptibility anisotropy originates from the z tensor axis lying in the heme plane, unlike all other heme systems investigated so far. This magnetic axis is almost exactly orthogonal to the axial histidine plane. The other two axes lie essentially in the histidine plane, the closest to the heme normal being tilted by about 36° from it, towards pyrrole A on the side of the proximal histidine. From the comparison with cytochrome c′ it clearly appears that the position of the one axis lying in the heme plane is related to the axial histidine orientation. Irrespective of the directions, the magnetic anisotropy is smaller than that of the analogous reduced cytochrome c′ and of the order of that of low‐spin iron(III). The magnetic anisotropy of the system permits the measurement of residual dipolar couplings, which, together with pseudocontact shifts, prove that the solution structure is very similar to that in the crystalline state. Magnetic measurements, at variance with previous data, demonstrate that there is an orbital contribution to the magnetic moment, μeff=5.5 μB. Finally, from the magnetic anisotropy data, the hyperfine shifts of iron ligands could be separated in pseudocontact and contact components, and hints are provided to understand the spin‐delocalisation mechanism in S=2 systems by keeping in mind the delocalisation patterns in low‐spin S=1/2 and high‐spin S= 5/2 iron(III) systems.
Synthesis and Reactions of Terminal Osmium and Ruthenium Complexed Phosphinidenes [(η6‐Ar)(L)MPMes*]
Authors: Termaten Arjan T. , Nijbacker Tom , Schakel Marius , Lutz Martin , Spek Anthony L. , Lammertsma Koop 
Published: May 2003

AbstractNovel, very stable ruthenium and osmium containing terminal phosphinidene complexes [(η6‐Ar)(L)MPMes*] (Ar=benzene, p‐cymene; L=PR3, CO, and RNC) have been prepared by dehydrohalogenation of novel [(η6‐Ar)MX2(PH2Mes*)] complexes in the presence of a stabilizing ligand. Xray crystal structures are reported for [(η6‐C6H6)(PPh3)RuPMes*] (9) and [(η6‐pCy)(PPh3)OsPMes*] (4). Dehydrohalogenation in the absence of a stabilizing ligand resulted in the new Pspiroannulated Ru2P2‐ring structure 16. Dehydrohalogenation in the presence of but‐2‐yne gave a novel phosphaallyl complex [(η6‐Ar)Ru(η3‐R2PC(Me)CHMe)] 26, for which an Xray crystal structure is reported. The mechanism by which 16 and 26 are obtained is presumed to involve the intermediate formation of the 16‐electron (η6‐benzene)RuPMes* phosphinidene complex.
Molecular Nitrides Containing Group 4 and 5 Metals: Single and Double Azatitanocubanes
Authors: Abarca Angel , Galakhov Mikhail V. , Gracia José , Martín Avelino , Mena Miguel , Poblet Josep‐M. , Sarasa José P. , Yélamos Carlos 
Published: May 2003

AbstractTreatment of [{Ti(η5‐C5Me5)(μ‐NH)}3(μ3‐N)] (1) with the imido complexes [Ti(NAr)Cl2(py)3] (Ar=2,4,6‐C6H2Me3) and [Ti(NtBu)Cl2(py)3] in toluene affords the single azatitanocubanes [{Cl2(ArN)Ti}(μ3‐NH)3{Ti3(η5‐C5Me5)3(μ3‐N)}]⋅(C7H8) (2⋅C7H8) and [{Cl2Ti}(μ3‐N)2(μ3‐NH){Ti3(η5‐C5Me5)3(μ3‐N)}] (3), respectively. Similar reactions of complex 1 with the niobium and tantalum imido derivatives [{M(NtBu)(NHtBu)Cl2(NH2tBu)}2] (M=Nb, Ta) in toluene give the single azaheterometallocubanes [{Cl2(tBuN)M}(μ3‐N)(μ3‐NH)2{Ti3(η5‐C5Me5)3(μ3‐N)}] (M=Nb (4), Ta (5)), both complexes react with 2,4,6‐trimethylaniline to yield the analogous species [{Cl2(ArN)M}(μ3‐N)(μ3‐NH)2{Ti3(η5‐C5Me5)3(μ3‐N)}]⋅(C7H8) (Ar=2,4,6‐C6H2Me3, M=Nb (6⋅C7H8), Ta (7⋅C7H8)). Also the azaheterodicubanes [M{(μ3‐N)2(μ3‐NH)}2{Ti3(η5‐C5Me5)3(μ3‐N)}2]⋅2C7H8 [M=Ti (8⋅2C7H8), Zr (9⋅2C7H8)], and [M{(μ3‐N)5(μ3‐NH)}{Ti3(η5‐C5Me5)3(μ3‐N)}2]⋅2 C7H8 (Nb (10⋅2C7H8), Ta (11⋅2C7H8)) were prepared from 1 and the homoleptic dimethylamido complex [M(NMe2)x] (x=4, M=Ti, Zr; x=5, M=Nb, Ta) in toluene at 150 °C. Xray crystal structure determinations were performed for 6 and 10, which revealed a cube‐ and double‐cube‐type core, respectively. For complexes 2 and 4–7 we observed and studied by DNMR a rotation or trigonal‐twist of the organometallic ligands [{Ti(η5‐C5Me5)(μ‐NH)}3(μ3‐N)] (1) and [(μ3‐N)(μ3‐NH)2{Ti3(η5‐C5Me5)3(μ3‐N)}]1−. Density functional theory calculations were carried out on model complexes of 2, 3, and 8 to establish and understand their structures.
Novel Conformationally Locked Inositols: From Aromatics to Annulated Cyclitols
Authors: Mehta Goverdhan , Senaiar Ramesh S. , Bera Mrinal K. 
Published: May 2003

AbstractA new family of ring‐annulated inositols with “locked” conformations has been designed to deliver a range of these biologically important entities in “unnatural conformations” while retaining their “natural configurations”. The simple “tool” of trans ring fusion has been used to “lock” the conformation of the annulated inositols. Short, simple syntheses of a range of these novel cyclitols have been achieved from readily available aromatic precursors such as tetralin and indane. Along the way, annulated C2‐symmetric cyclohexadiene‐trans‐diol (trans‐CHD) derivatives have been prepared for the first time and serve as the pivotal building blocks for generating the oxy‐functionalization pattern of inositols. The presence of chemo‐differentiated hydroxyl groups in our novel inositols is expected to facilitate the installation of phosphate diversity to harness the biological potential of these entities.
ThioformaldehydeS‐Methylide and ThioacetoneS‐Methylide: An Ab Initio MO Study of Structure and Cycloaddition Reactivity
Authors: Sustmann Reiner , Sicking Willi , Huisgen Rolf 
Published: May 2003

AbstractThe mechanisms of cycloaddition of thioformaldehydeS‐methylide and thioacetoneS‐methylide, as models for an alkyl‐substituted ylide, to thioformaldehyde and thioacetone, as well as to ethene as a model for a CC double bond have been studied by ab initio calculations. Restricted and unrestricted B3LYP/6–31G* calculations were performed for the geometries of ground states, transition structures, and intermediates. Although basis sets with more polarization functions were tested, the 6–31G* basis set was applied throughout. Single‐point CASPT2 calculations are reported for analysis of the unsubstituted system. The stabilities of structures with high biradical character seem to be overestimated by DFT methods in comparison to CASPT2. The general trends of the results are independent of the level of theory. Thioformaldehyde adds to thioformaldehydeS‐methylide without activation energy, and the activation energies for two‐step biradical pathways to 1,3‐dithiolane are low.C,Sbiradicals are more stable thanC,Cbiradicals. The two‐step cycloaddition is not competitive with the concerted cycloaddition. Methyl substitution in the 1,3‐dipole and the dipolarophile does not change the mechanistic relationships. TSs for the concerted formation of the regioisomeric cycloadducts of thioacetoneSmethylide and thioacetone were located. Concerted addition remains the preferred reaction. The reactivity of the CS double bond is high relative to that of the CC double bond.
Structure–Nucleophilicity Relationships for Enamines
Authors: Kempf Bernhard , Hampel Nathalie , Ofial Armin R. , Mayr Herbert 
Published: May 2003

AbstractThe kinetics of the reactions of benzhydryl cations with 22 enamines, three pyrroles, and three indoles were investigated photometrically in dichloromethane. The nucleophilicity parameters N and slope parameters s of these electron‐rich π‐systems were derived from equation log k (20 °C)=s(E+N) and compared with the nucleophilicities of other π‐systems (silyl enol ethers, silyl ketene acetals) and carbanions. It is shown that the nucleophilic reactivities of enamines cover more than ten orders of magnitude, comparable to enol ethers on the low reactivity end and to carbanions on the high reactivity end. Since the products of Nattack are thermodynamically less stable than the reactants, the observed rate constants refer to the formation of the carbon carbon bonds. In some cases, equilibrium constants for the formation of iminium ions were measured, which allow one to determine the intrinsic rate constants of these reactions.
Unusual Coupling Reactions of Aldehydes and Alkynes: A Novel Preparation of Substituted Phthalic Acid Derivatives by Automated Synthesis
Authors: Jacobi von Wangelin Axel , Neumann Helfried , Gördes Dirk , Klaus Stefan , Jiao Haijun , Spannenberg Anke , Krüger Thomas , Wendler Christian , Thurow Kerstin , Stoll Norbert , Beller Matthias 
Published: May 2003

AbstractBased upon a highly versatile multicomponent methodology, a new one‐pot synthesis of substituted phthalic acid derivatives from α,β‐unsaturated aldehydes was developed. The reaction involves the intermediacy of an acetamidodiene species which undergoes Diels–Alder addition to diethyl acetylenedicarboxylate. The resultant acetamidocyclohexadiene is subject to elimination of acetamide under the reaction conditions to give rise to substituted diethyl phthalates in good yields. This domino condensation–cycloaddition–elimination sequence has been applied to a variety of α,β‐unsaturated aldehydes. Furthermore, we demonstrated the exploitation of parallelized and automated synthesis technology for the rapid screening of reaction conditions and compositions. Detailed studies revealed the catalytic role of the employed acetamide and the occurrence of a stereoselective 1,4‐syn elimination pathway under standard conditions.