Transannular π-cyclization in electrophilic additions to 1,5-dimethylcycloocta-1,5-diene

Electrophilic additions of Broensted acids to 1,5-dimethylcycloocta-1,5-diene yield syn-8-substituted 1,5-dimethylbicyclo [3.2.1] octanes via parallel π-cyclization and subsequent Wagner-Meerwein type rearrangements. The corresponding anti-isomers are synthesized by nucleophilic substitution in the 8-position. The classical or nonclassical structure of the cationic intermediates is discussed.     

Diels-Alder Reactions of Ethyl α-Bromoacrylate with Open-chain Dienes——Synthesis of Ethyl 1,3-/1,4-Cyclohexadienecarboxylates

The Diels‐Alder reactions of ethyl α‐bromoacrylate 1 with open‐chain dienes 2 were conducted under thermal or Lewis acid‐catalysis conditions. In most cases, the cyclic adducts of 1‐bromocyclohex‐3‐enecarboxylates 3 were formed in high yields with good regio‐ and stereoselectivity. Subsequent E2‐elimination by treatment with DBU provided the corresponding 1,3‐ or 1,4‐cyclohexadienecarboxylates depending on the relative configuration of the products. Starting from myrcene (7‐methyl‐3‐methyleneocta‐1,6‐diene) the reaction sequence afforded the ester precursor of Georgywood with good yields.     

From Very Strong to Inexistent Be−Be Bonds in the Interactions of Be2 with π-Systems

Isolated Be₂ is a typical example of a weakly bound system, but interaction with other systems may give rise to surprising bonding features. The interactions between Be₂ and a set of selected neutral C_nH_n (n=2–8) π-systems have been analyzed through the use of G4 and G4MP2 ab initio methods, along with multireference CASPT2//CASPT2 calculations. Our results systematically show that the C_nH_n−Be₂−C_nH_n clusters formed are always very stable. However, the nature of this interaction is completely different when the π-system involved is a closed shell species (n=2, 4, 6, 8), or a radical (n=3, 5, 7). In the first case, the interaction does not occur with the π-system as a whole, but with specific C centers yielding rather polar but strong C−Be bonds. Nonetheless, although the Be−Be distances in these complexes are similar to the ones in compounds with ultra-strong Be−Be bonds, a close examination of their electron density distribution reveals that no Be−Be bonds exist. The situation is totally different when the interaction involves two π-radicals, C_nH_n−Be₂−C_nH_n (n=3, 5, 7). In these cases, a strong Be−Be bond is formed. Indeed, even though Be is electron deficient, the Be₂ moiety behaves as an efficient electron donor towards the two π-radicals, so that the different C_nH_n−Be₂−C_nH_n (n=3, 5, 7) clusters are the result of the interaction between Be₂²⁺ and two L⁻ anions. The characteristics of these two scenarios do not change when dealing with bicyclic π-compounds, such as naphthalene and pentalene, because the interaction with the Be₂ moiety is localized on one of the unsaturated cycles, the other being almost a spectator.     

Utility of 2-Diphenylphosphoryloxy-1,3-Dienes in Multicomponent Hetero-Diels–Alder Reactions to Construct Functionalized Six-Membered Nitrogen Heterocycles

The utility of 2-diphenylphosphoryloxy-1,3-dienes for the construction of substituted six-membered nitrogen heterocycles is presented. These dienes undergo boron trifluoride-promoted aza-Diels–Alder reactions when reacted with imines or related species formed in situ using aldehydes and amine derivatives. The stability of the dienes allows this three-component reaction to be carried out with no special precautions to eliminate water or air. Thirty-one examples of this process are presented. The usefulness of the enol phosphate functional group is highlighted in further reactions after the cycloaddition step to generate functionalized piperidenes or pyridines.     

Chemical Reactions and Kinetics of the Carbon Monoxide Coupling in the Presence of Hydrogen

The chemical reactions and kinetics of the catalytic coupling reaction of carbon monoxide to diethyl oxalate were studied in the presence of hydrogen over a supported palladium catalyst in the gaseous phase at the typical coupling reaction conditions. The experiments were performed in a continuous flow fixed-bed reactor. The results indicated that hydrogen only reacts with ethyl nitrite to form ethanol, and kinetic studies revealed that the rate-determining step is the surface reaction of adsorbed hydrogen and the ethoxy radical (EtO-). A kinetic model is proposed and a comparison of the observed and calculated conversions showed that the rate expressions are of rather high confidence.     

Base-Selective Five- versus Six-Membered Ring Annulation in Palladium-Catalyzed C–C Coupling Cascade Reactions: New Access to Electron-Poor Polycyclic Aromatic Dicarboximides

Palladium-catalyzed base-selective annulation of dibromonaphthalimide to different aryl boronate esters by combined Suzuki–Miyaura cross-coupling and direct C−H arylation afforded a series of new five- and six-membered ring annulated electron-poor polycyclic aromatic hydrocarbons. Cesium carbonate (Cs₂CO₃) as auxiliary base in these C−C coupling cascade reactions led exclusively to six-membered ring annulation, while the use of organic base diazabicycloundecene (DBU) afforded the corresponding five-membered ring annulated products. This base-dependent selective mode of annulation is attributed to different mechanistic pathways directed by the applied base. The selective annulation was revealed by single crystal X-ray analysis of the respective five- and six-membered ring annulated products. The optical and redox properties of the new polycyclic aromatic dicarboximides were characterized by UV/Vis absorption and fluorescence spectroscopy and cyclic voltammetry.     

Cycloaddition Chemistry of a Silylene-Nickel Complex toward Organic π-Systems: From Reversibility to C−H Activation

The versatile cycloaddition chemistry of the Si−Ni multiple bond in the acyclic (amido)(chloro)silylene→Ni⁰ complex 1 , [(^TMSL)ClSi→Ni(NHC)₂] (^TMSL=N(SiMe₃)Dipp; Dipp=2,6-iPr₂C₆H₄; NHC=C[(iPr)NC(Me)]₂), toward unsaturated organic substrates is reported, which is both reminiscent of and expanding on the reactivity patterns of classical Fischer and Schrock carbene–metal complexes. Thus, 1:1 reaction of 1 with aldehydes, imines, alkynes, and even alkenes proceed to yield [2+2] cycloaddition products, leading to a range of four-membered metallasilacycles. This cycloaddition is in fact reversible for ethylene, whereas addition of an excess of this olefin leads to quantitative sp²-CH bond activation, via a 1-nickela-4-silacyclohexane intermediate. These results have been supported by DFT calculations giving insights into key mechanistic aspects.     

Access to β-Ketonitriles through Nickel-Catalyzed Carbonylative Coupling of α-Bromonitriles with Alkylzinc Reagents

Herein, we report a nickel-catalyzed carbonylative coupling of α-bromonitriles and alkylzinc reagents with near stoichiometric carbon monoxide to give β-ketonitriles in good yields. The reaction is catalyzed by a readily available and stable nickel(II) pincer complex. The developed protocol tolerates substrates bearing a variety of functional groups, which would be problematic or incompatible with previous synthetic methods. Additionally, we demonstrate the suitability of the method for carbon isotope labeling by the synthesis of ¹³C-labeled β-ketonitriles and their transformation into isotopically labeled heterocycles.     

On the Acidity and Lithiation-Functionalization of Thiophenes: Revisited for their Use in the Synthesis of Thiophene-Based Novel π-Systems

When lithium diisopropylamide is used for lithiation and functionalization of thiophenes, whose acidity is here measured to be pKa = 35-36 in THF-Hex (5:3), the equilibrated nature of lithiation is to be taken into consideration.     

Alkali-Metal Aminotroponiminates: Selectivities and Equilibria in Reversible Radical Coupling of Delocalized π-Electron Systems

Aminotroponiminates (ATIs) have recently been shown to belong to the growing class of redox-active ligands. The choice of the metal center allowed to switch between reversible electron transfer (M=Rh) and reductively induced dimerization (M=Na). Here, we investigate if the reductively induced dimerization of ATIs is a more general phenomenon for their alkali-metal complexes. Lithium ATI complexes are shown to undergo reductively induced dimerizations, which are equilibrium reactions and chemically reversible. The choice of the metal center (Li vs. Na), the substitution pattern at the nitrogen atoms of the ATI ligands, and the solvent critically influence the regioselectivity and diastereoselectivity of the radical-dimerization reactions. Potassium ATIs are shown to be susceptible to side reactions, more specifically a reduction accompanied by hydrogen-atom transfer. Products and intermediates of the reductively induced dimerizations were characterized by techniques including NMR and EPR spectroscopy, cyclic voltammetry, DFT calculations, single-crystal X-ray diffraction, and mass spectrometry.     

Coupling of Methyl Ketones and Primary or Secondary Amines Leading to α-Ketoamides

A metal-free oxidative coupling of methyl ketones and primary or secondary amines to α-ketoamides has been developed. Four intermediates, α-iodoketone, α-aminoketone, iminium intermediate, and α-hydroxy amine have been identified through a series of control experiments. The atom-economic methodology can be scaled-up, tolerates a variety of functional groups, and is operationally simple.     

Substituent Effects on Hyperfine Coupling Constants Analyzed in Terms of π-Bound Electron Perturbation Theory

Substituent effects on the hyperfine interaction (hfi) constants of hydrocarbon, quinone, aza-, and hydroazaaromatic radicals are analyzed in terms of -bound electron perturbation theory. For odd alternant radicals, substituent effects are described in terms of second-order perturbation theory using a quadratic dependence on the constants of the substituents. The results of the calculation agree well with the available experimental data.     

Formation of π-excimer or π-exciplex in electrogenerated chemiluminescence involving perylene molecule revealed using a dual-electrolysis stopped-flow method

Electrogenerated chemiluminescence (ECL) reactions involving the perylene cation radical (PE⁺) and perylene anion radical (PE⁻) in acetonitrile have been observed using a dual-electrolysis stopped-flow method. In this method, ECL emission from the systems composed of different kinds of ion radicals can be easily observed by mixing both the electrolyzed solutions directly. Therefore, the ECL spectra were observed systematically in the reactions of PE⁺ and PE⁻ with different ion radicals. Consequently, emission definitely from the singlet state of PE was observed in the reactions between PE⁺ and the 9,10-diphenylanthracene anion radical (DPA⁻), PE⁻ and DPA⁺, and PE⁻ and the thianthrene cation radical (TH⁺). In contrast, emission at long wavelength was obtained in the reaction between PE⁺ and the pyrene anion radical (PY⁻) as well as the reaction between PE⁺ and PE⁻. From this result, for the molecular interactions involving PE and PY, the presence of the π complexing interaction to form the π-excimer and the π-exciplex was strongly suggested in the ECL-emitting reactions. The present approach was thus found to be effective to reveal the molecular aspects of the excited states formed in solution.     

Reaction of aminals of conjugated unsaturated ω-dimethylaminoaldehydes with 1,2-, 1,3-, 1,4-, 1,5-, and 1,6-diketones

The condensation of aminals of -dimethylaminoacrolein and 5-dimethylaminopenta-2,4-dienal with cyclic and acyclic 1,2-, 1,3-, 1,4-, 1,5-, and 1,6-diketones was studied. A series of previously unknown bis(,-dimethylaminopolyenyl)diketones was synthesized; their structures were established by means of¹H and¹³C NMR spectroscopies. The electron absorption spectra were employed to study the mutual influence of -aminopolyene chromophores separated by two C=O groups.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1235–1241, July, 1993.     

Inclusion of dynamic σ-π polarization in π-electronab initio calculations

Summary A method is presented, whereby dynamic - polarization, i.e. the correlation effect expressed by simultaneous (-*, -*) excitations, can be approximately included in a multi-reference configuration interaction (MRCI) or multi-configurational self-consistent field (MC-SCF) calculation, without need to explicitly correlate the sigma orbitals. The method, which we call the capacitance matrix method, is based on the use of conventional one-electron integrals, from which a polarization potential (SPP) contribution is computed and added to the one- and two-electron Hamiltonian. In the present form, the method requires one parameter for each type of atom, and one for each type of bond. These parameters were adjusted to reproduce the dynamic - polarization energy, computed by restricted multi-reference CI calculations, of a number of states of different hydrocarbons, and the agreement was within a few percent. Using the same parameters in CAS (Complete Active Space) SCF calculations of various states of benzene gives excitation energies, when SPP is included, which is comparable to those obtained by much more elaborate MRCI calculations.     

Modulation of the Self-Assembly of π-Amphiphiles in Water from Enthalpy- to Entropy-Driven by Enwrapping Substituents

Depending on the connectivity of solubilizing oligoethylene glycol (OEG) side chains to the π-cores of amphiphilic naphthalene and perylene bisimide dyes, self-assembly in water occurs either upon heating or cooling. Herein, we show that this effect originates from differences in the enwrapping capability of the π-cores by the OEG chains. Rylene bisimides bearing phenyl substituents with three OEG chains attached directly to the hydrophobic π-cores are strongly sequestered by the OEG chains. These molecules self-assemble at elevated temperatures in an entropy-driven process according to temperature- and concentration-dependent UV/Vis spectroscopy and calorimetric dilution studies. In contrast, for rylene bisimides in which phenyl substituents with three OEG chains are attached via a methylene spacer, leading to much weaker sequestration, self-assembly originates upon cooling in an enthalpy-driven process. Our explanation for this controversial behavior is that the aggregation in the latter case is dictated by the release of “high energy water” from the hydrophobic π-surfaces as well as dispersion interactions between the π-scaffolds which drive the self-assembly in an enthalpically driven process. In contrast, for the former case we suggest that in addition to the conventional explanation of a dehydration of hydrogen-bonded water molecules from OEG units it is in particular the increase in conformational entropy of back-folded OEG side chains upon aggregation that provides the pronounced gain in entropy that drives the aggregation process. Thus, our studies revealed that a subtle change in the attachment of solubilizing substituents can switch the thermodynamic signature for the self-assembly of amphiphilic dyes in water from enthalpy- to entropy-driven.     

Structure and catalytic activity of host–guest coordination polymers constructed from copper(I) cyanide nets and 1,4-diaminobutane or 1,5-diaminopentane in the presence of water

The reaction of K₃[Cu(CN)₄] and 1,4-diaminobutane (DAB) or 1,5-diaminopentane (DAP) in the presence of Me₃SnCl affords two monometallic host–guest Cu(I) cyanide polymers: {[H₂DAB][Cu₄(CN)₆]·2H₂O}, 1, and{[H₂DAP][H₃O][Cu₄(CN)₇]·2H₂O}, 2, with exclusion of Me₃Sn⁺ cation. The products were characterized by physicochemical and spectroscopic methods. The structure of 1 consists of two-dimensional hexagonal sheets of (CuCN) _n which stack along the b-axis creating honeycomb-shaped channels capable of encapsulating the protonated DAB and water molecules. The structure of 2 consists of a three-dimensional network of [Cu₄(CN)₇] with large cavities that include H₂DAP and water molecules. The rhombic minicycle [Cu₂(μ-CN)₂] fragments represent the basic building blocks of the network structure of 2. The structures of these compounds are stabilized by hydrogen bonding. The SCP 1 and SCP 2 exhibit good catalytic and photocatalytic activities for the degradation of methylene blue (MB) in the presence of H₂O₂. The efficiency of recycled SCP 1 and SCP 2 and the mechanism of degradation of MB dye were also investigated.     

Rhodium-Catalyzed Copper-Assisted Intermolecular Domino C−H Annulation of 1,3-Diynes with Picolinamides: Access to Pentacyclic π-Extended Systems

A new mode of reactivity of 1,3-diynes in rhodium-catalyzed oxidative annulation reactions has enabled the rapid assembly of extended π systems from readily available picolinamide derivatives. The process involves a double C−H bond activation and the iterative annulation of two 1,3-diyne units, with each alkyne moiety engaged in an orchestrated insertion sequence with high regiocontrol, leading to the formation of five new C−C bonds and the construction of four fused rings in a single operation. Either isoquinoline-1-carboxamides or fused polycyclic systems can be accessed by a switch in the regioselectivity of the second diyne insertion depending on the reaction conditions. DFT theoretical calculations have elucidated that the cooperative participation of both rhodium and copper in substrate activation, favored in the presence of excess of the copper(II) salt, is key to such a reversal of regioselectivity and subsequent multiple cyclization leading to fused polycyclic products. The role of copper was found to be essential in assisting both multiple insertion and rhodium-walking sequences, with the implication of intermediates with a Rh−Cu bond (2.60 Å).