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Substituents
Kinds of Substituents Terms modified by Substituents Selected AbstractsEnantio- and Diastereomerically Pure Decalins by Deslongchamps-Type Annulation of Dienolates Containing a Chiral Lactone SubstituentEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 7 2007Thomas Tricotet Abstract A conceptionally novel 1,3-asymmetric induction has been established. It controls the relative and absolute configuration of up to 5 stereocenters. They emerge from the anionic Diels,Alder reactions ("Deslongchamps annulations") between oxocyclohexenecarboxylates 25, 29 and dienolates 26, 30. The latter contain a ,-lactone. A Ph3Si,CH2 substituent therein controls the asymmetry of C,C bond formation with ds , 10:1. Strangely, the preferred sense of attack of the dienophile is contrasteric. Cycloadduct 31 was processed by an unprecedented fluoride-induced ambient-temperature tandem fragmentation. It turned the lactone moiety into an allyl group and the ,-oxo (trimethylsilyl)ethyl ester into a ketone. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Direct Introduction of a Boryl Substituent into the 2-Position of Azulene: Application of the Miyaura and Smith Methods to AzuleneEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 18 2003Kei Kurotobi Abstract The 4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl group was directly introduced into the 2-positions of azulenes with high selectivity by the C,H activation method with use of iridium catalysis. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Effect of Carbon Chain Length in the Substituent of PCBM-like Molecules on Their Photovoltaic PropertiesADVANCED FUNCTIONAL MATERIALS, Issue 9 2010Guangjin Zhao Abstract A series of [6,6]-phenyl-C61 -butyric acid methyl ester (PCBM)-like fullerene derivatives with the butyl chain in PCBM changing from 3 to 7 carbon atoms, respectively (F1,F5), are designed and synthesized to investigate the relationship between photovoltaic properties and the molecular structure of fullerene derivative acceptors. F2 with a butyl chain is PCBM itself for comparison. Electrochemical, optical, electron mobility, morphology, and photovoltaic properties of the molecules are characterized, and the effect of the alkyl chain length on their properties is investigated. Although there is little difference in the absorption spectra and LUMO energy levels of F1,F5, an interesting effect of the alkyl chain length on the photovoltaic properties is observed. For the polymer solar cells (PSCs) based on P3HT as donor and F1,F5, respectively, as acceptors, the photovoltaic behavior of the P3HT/F1 and P3HT/F4 systems are similar to or a little better than that of the P3HT/PCBM device with power conversion efficiencies (PCEs) above 3.5%, while the performances of P3HT/F3 and P3HT/F5-based solar cells are poorer, with PCE values below 3.0%. The phenomenon is explained by the effect of the alkyl chain length on the absorption spectra, fluorescence quenching degree, electron mobility, and morphology of the P3HT/F1,F5 (1:1, w/w) blend films. [source] S. Kumaresan and P. Kannan, "Substituent effect on azobenzene-based liquid-crystalline organophosphorus polymers" Journal of Polymer Science Part A: Polymer Chemistry (2003) 41(20) 3188,3196JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 23 2003S. Kumaresan The original article to which this Erratum refers was published inJournal of Polymer Science Part A: Polymer Chemistry (2003) 41(20) 3188,3196 No abstract. [source] Novel Triaromatic Ester Mesogenic Liquid Crystalline Epoxy Resin Containing Both Methyl Substituent and Ethoxy Flexible Spacer: Synthesis and CuringMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 11 2008Guo-dong Liu Abstract A novel triaromatic ester liquid crystalline epoxy resin (LCER) that contains both a methyl substituent and an ethoxy flexible spacer, p -methylphenylene di{4-[(2,3-epoxypropoxy)ethoxy]benzoate} (MPEPEB), has been synthesized. The mesotropic property has been investigated by differential scanning calorimetry (DSC) and polarized light optical microscopy (POM). MPEPEB shows a lower melting temperature at 78.7,°C and a broad nematic mesophase temperature range of about 55,°C. Meanwhile MPEPEB shows a mesophase to ,50,°C upon cooling. The curing behavior of MPEPEB with 2,6-diamino-3,5-diethyltoluene (DAE) has been investigated by means of DSC and POM during isothermal and dynamic processes. Although there is little difference between the activation energies obtained from the kinetic data, a marked difference is found between the isothermal and dynamic investigation. The curing reaction in the isothermal investigation roughly obeys n- th order kinetics, while two exothermal peaks appear in the dynamic DSC curves of MPEPEB/DAE. A comparison of the isothermal and dynamic data shows that the curing rate is not a unique function of temperature and curing degree. The cured networks have lower glass temperatures and show a mesophase at room temperature which disappears at about 86,88,°C. [source] ChemInform Abstract: Expeditious Synthesis of Benzopyrans via Lewis Acid-Catalyzed C,H Functionalization: Remarkable Enhancement of Reactivity by an ortho Substituent.CHEMINFORM, Issue 34 2010Keiji Mori Abstract ortho-Substitution to the alkoxy group enhances the reactivity of the substrates and leads to the higher yields of the corresponding products [cf. [source] ChemInform Abstract: Conversion of 3-Arylphthalides into Anthrones with a Methylcarbonyl Substituent at the C-10 Position.CHEMINFORM, Issue 33 2009Adam Bieniek Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] ChemInform Abstract: Exploring Modular Domino Reactions: Competing Processes Based on the Nature of the Angular Substituent.CHEMINFORM, Issue 14 2008Zobida Elkhayat Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Synthesis of 2,4,5-Trisubstituted Thiazoles with a 5-(N,N-Dimethylaminomethyl) Substituent.CHEMINFORM, Issue 39 2007Bernhard Stump Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Asymmetric Route to Pyridines Bearing a Highly Functionalized 2-Alkyl Substituent by Aziridine Ring-Opening Reactions.CHEMINFORM, Issue 37 2007Diego Savoia Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] A Novel Synthetic Approach to Benzo[d]isothiazole 1,1-Diones Having a Secondary Alkyl Substituent at the 3-Position.CHEMINFORM, Issue 30 2004Zhaopeng Liu Abstract For Abstract see ChemInform Abstract in Full Text. [source] The First Generation of Azulenyl-Lithium and -Magnesium: A Novel, Versatile Method of Introducing a Substituent at the 2-Position of an Azulene Skeleton.CHEMINFORM, Issue 16 2003Kei Kurotobi No abstract is available for this article. [source] Preparation and Properties of Fluorenylidenephosphines Bearing an Electron-Donating Substituent, 2-Alkoxy-4,6-di-t-butylphenyl (Ia) or 2-(Alkoxymethyl)-4,6-di-t-butylphenyl (Ib).CHEMINFORM, Issue 3 2003Kozo Toyota No abstract is available for this article. [source] ChemInform Abstract: Enzyme-Mediated Enantioselective Hydrolysis of Cyclic Carbonates Bearing an Unsaturated Substituent.CHEMINFORM, Issue 49 2002Kazutsugu Matsumoto Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] ChemInform Abstract: Synthesis and Antihypertensive Activities of New 1,4-Dihydropyridine Containing Nitroimidazolyl Substituent with a Nitrooxy Group at the 3-Ester Position.CHEMINFORM, Issue 34 2002Abbas Shafiee Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] ChemInform Abstract: [60]Fullerene as a Substituent.CHEMINFORM, Issue 29 2002Alessandro Gagno Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] ChemInform Abstract: The Reaction of ,-Amino Alcohols with 1,1,-Carbonyldiimidazole , Influence of the Nitrogen Substituent on the Reaction Course.CHEMINFORM, Issue 11 2002Sara Cutugno Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] ChemInform Abstract: Oxazolinylferrocene Ligands for the Addition of Diethylzinc to Benzaldehyde: Effects of the Symmetry and the Substituent on the Oxazoline Ring of the Ligands on Asymmetric Catalysis.CHEMINFORM, Issue 5 2001Wanbin Zhang Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Effect of the Nature of the Substituent in N -Alkylimidazole Ligands on the Outcome of Deprotonation: Ring Opening versus the Formation of N-Heterocyclic Carbene ComplexesCHEMISTRY - A EUROPEAN JOURNAL, Issue 28 2010Miguel Abstract Complexes [Re(CO)3(N -RIm)3]OTf (N -RIm=N -alkylimidazole, OTf=trifluoromethanesulfonate; 1,a,d) have been straightforwardly synthesised from [Re(OTf)(CO)5] and the appropriate N -alkylimidazole. The reaction of compounds 1,a,d with the strong base KN(SiMe3)2 led to deprotonation of a central CH group of an imidazole ligand, thus affording very highly reactive derivatives. The latter can evolve through two different pathways, depending on the nature of the substituents of the imidazole ligands. Compound 1,a contains three N -MeIm ligands, and its product 2,a features a C-bound imidazol-2-yl ligand. When 2,a is treated with HOTf or MeOTf, rhenium N-heterocyclic carbenes (NHCs) 3,a or 4,a are afforded as a result of the protonation or methylation, respectively, of the non-coordinated N atom. The reaction of 2,a with [AuCl(PPh3)] led to the heterobimetallic compound 5, in which the N-heterocyclic ligand is once again N-bound to the Re atom and C-coordinated to the gold fragment. For compounds 1,b,d, with at least one N -arylimidazole ligand, deprotonation led to an unprecedented reactivity pattern: the carbanion generated by the deprotonation of the C2H group of an imidazole ligand attacks a central CH group of a neighbouring N -RIm ligand, thus affording the product of CC coupling and ring-opening of the imidazole moiety that has been attacked (2,c,,d). The new complexes featured an amido-type N atom that can be protonated or methylated, thus obtaining compounds 3,c,,d or 4,c,,d, respectively. The latter reaction forces a change in the disposition of the olefinic unit generated by the ring-opening of the N -RIm ligand from a cisoid to a transoid geometry. Theoretical calculations help to rationalise the experimental observation of ring-opening (when at least one of the substituents of the imidazole ligands is an aryl group) or tautomerisation of the N-heterocyclic ligand to afford the imidazol-2-yl product. [source] Preparation and Reactions of 1,3-Diphosphacyclobutane-2,4-diyls That Feature an Amino Substituent and/or a Carbonyl GroupCHEMISTRY - A EUROPEAN JOURNAL, Issue 11 2004Hiroki Sugiyama Abstract The preparation and properties of a 1-amino-1,3-diphosphacyclobutane-2,4-diyl and a 1-benzoyl-1,3-diphosphacyclobutane-2,4-diyl, which can be regarded as functionalized cyclic biradical derivatives, were investigated. Hydrolysis of 1-diisopropylamino-3-methyl-2,4-bis(2,4,6-tri- tert -butylphenyl)-1,3-diphosphacyclobutane-2,4-diyl (7), which is formed by reaction of Mes*CP (4; Mes*=2,4,6- tBu3C6H2) with lithium diisopropylamide and iodomethane, resulted in ring-opening of the 1,3-diphosphacyclobutane-2,4-diyl skeleton, as well as de-aromatization of one of the Mes* rings. 3-Oxo-1,3-diphosphapropene 8 and 7-phosphabicyclo[4.2.0]octa-1(8),2,4-triene 9 were the resultant products, and these were subsequently characterized. Isomerization and oxidation of 7 occurred in the presence of TEMPO (2,2,6,6-tetramethyl-1-piperidinoxy) to give the first example of a cyclic dimethylenephosphorane derivative, namely 3-oxo-1,3-diphospha-1,4-diene 10. 1-Benzoyl-3- tert -butyl-2,4-bis(2,4,6-tri -tert -butylphenyl)-1,3-diphosphacyclobutane-2,4-diyl (12) was isolated and characterized from the reaction of 4 with tert -butyllithium and benzoyl chloride. Compound 12 was subsequently heated and underwent rearrangement of the benzoyl group and ring-expansion to afford 1-oxo-1H -[1,3]diphosphole 13. Reaction of 4 with lithium diisopropylamide and benzoyl chloride afforded the 2H -[1,2,4]oxadiphosphinine 15, which was probably formed through the 1,3-diphosphacyclobutane-2,4-diyl intermediate 14. Thermolysis of 15 afforded 1-oxo-1H -[1,3]diphosphole 16 in an Arbuzov-type rearrangement. [source] Synthesis of Hafnacyclopentanes from Hafnocene Alkyne Complexes: Influence of Styrene Substituents on the C,C Coupling RegioselectivityEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 11 2009Torsten Beweries Abstract The alkyne complex rac -(ebthi)Hf(,2 -Me3SiC2SiMe3) (1)[ebthi = 1,2-ethylene-1,1,-bis(,5 -tetrahydroindenyl)] reacts with styrene and p -(trifluoromethyl)styrene to give hafnacyclopentanes 2 and 3, respectively. C,C coupling proceeds in different ways: whereas for complex 2 a hafnacyclopentane with substituents in the ,,,-position is formed, in the latter case only ,,, coupling was observed. Complexes 2 and 3 can be activated with B(C6F5)3 to form active catalysts for the polymerization of ethylene.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Using Chiral Ligand Substituents To Promote the Formation of Dinuclear, Double-Stranded Iron, Manganese, and Zinc MesocatesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 33 2007Stuart D. Reid Abstract The synthesis and structures of dinuclear manganese, iron, and zinc complexes of chiral di-iminodipyrromethane ligands (L) are reported. Schiff base condensation reactions between 5,5,-diformyl-2,2,-dipyrromethane and the chiral amines (,)-(R)-CH(Me)tBu and (+)-(R)-CH(Me)Ph result in the straightforward synthesis of the new, chiral ligands H2L2 and H2L3, respectively. Salt elimination reactions between K2L and divalent Mn and Fe halides, and protonolysis reactions between ZnMe2 and H2L result in the formation of the new dinuclear complexes [M2(L)2]. Investigation of the structures of these compounds in solution and in the solid state reveal that chiral mesocates are formed for L = L2, whereas for L = L3, a racemic mixture of helicates is present.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] First-Row Transition Metal Bis(amidinate) Complexes; Planar Four-Coordination of FeII Enforced by Sterically Demanding Aryl SubstituentsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 11 2005Christian A. Nijhuis Abstract The sterically hindered benzamidinate ligand [PhC(NAr)2], (Ar = 2,6- iPr2C6H3) has been employed to prepare bis(amidinate) complexes [{PhC(NAr)2}2M] of the divalent first-row transition metals Cr,Ni (1,5). For Cr (planar), Mn and Co (tetrahedral) the observed structures follow the electronic preference for the metal ion in its highest spin multiplicity, as determined by DFT calculations. Remarkably, the Fe derivative adopts a distorted planar structure while retaining the high-spin (S = 2) configuration. This rare combination is due to reduced interligand steric interactions in the planar vs. the tetrahedral structure, combined with a relatively small electronic preference of FeII for the tetrahedral environment. Thus, the simple bidentate ligand N,N' -diarylbenzamidinate provides a convenient means to make this unusual species accessible for further study. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Bis(salicylaldiminato)titanium Complexes Containing Bulky Imine Substituents: Synthesis, Characterization and Ethene Polymerization StudiesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 11 2005Antti Pärssinen Abstract A series of titanium complexes bearing two anionic [N, O,] bidentate salicylaldiminato ligands, namely bis[(N -salicylidene)anilinato]titanium(IV) dichloride (1), bis[(N -salicylidene)-2,6-dimethylanilinato]titanium(IV) dichloride (2), bis[(N -salicylidene)-2,6-di- i - propylanilinato]titanium(IV) dichloride (3), bis[(N -salicylidene)-(1-naphthalenylimino)]titanium(IV) dichloride (4), bis[(N -salicylidene)-2,6-difluoroanilinato]titanium(IV) dichloride (5), and bis[(N -3-fluorosalicylidene)-2,6-difluoroanilinato]titanium(IV) dichloride (6) have been synthesized with good yields by a two-step procedure. The X-ray structure analysis reveals that in complex 2, titanium has a distorted octahedral coordination sphere in which the oxygen atoms and the chloride ligands form the basal plane. Both the chloride and the phenoxy moieties have a cis orientation and the angle between the chloride ligands is 93.05°. The imine nitrogen atoms complete the octahedral coordination of the Ti center by occupying the axial positions. The newly synthesized (2 and 4,6) and already known complexes (1 and 3) were introduced in detailed ethene-polymerization studies. The activities achieved were low to moderate depending on the size and nature of the imino substituents. The polyethenes (PEs) produced had high molar masses, and the modalities of the molecular weight distributions varyied with polymerization temperature. Based on the results of ab initio calculations and on the experimental data obtained, an explanation for uni- and bimodal polymerization behavior and the differences in catalytic activities are given. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Pyrazolate-Based Dinucleating Ligands in L2M2 Scaffolds: Effects of Bulky Substituents and Coligands on Structures and M···H,C InteractionsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 8 2004Jens C. Röder Abstract A series of nickel(II) and palladium(II) complexes [L2M2]2+ have been prepared and structurally characterized, where L is a pyrazolate ligand with bulky 2,6-dimethyl- or 2,6-di(isopropyl)anilinomethyl side arms. Coordinating counter anions such as chloride can bind to axial sites of the dinickel species in a solvent-dependent process, giving rise to five-coordinate high-spin metal ions. In the case of weakly coordinating anions, the metal ions are found in roughly square-planar environments, and the structures are governed by the tendency of the bulky aryl groups to avoid each other, which forces the methyl or isopropyl substituents in the aryl 2- and 6-positions to approach the metal ions from the axial directions. This leads to drastic low-field shifts of the respective 1H NMR signals, e.g. , = 7.86 ppm for the isopropyl ,CH which comes in close proximity to the low-spin nickel(II) center. The relevance of such low-field NMR resonances of protons close to the axial sites of d8 metal ions for possible three-center four-electron M···H,C hydrogen bonds involving the filled d orbital of the metal ion is discussed. In the present case, attractive M···H interactions are assumed to be of no major significance. This was corroborated by the structure of a further [L2Ni2]2+ type complex where the anilinomethyl side arms bear only a single 2-isopropyl group, which was found rotated away from the metal. Additional spectroscopic and electrochemical properties of the various complexes are reported. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Synthesis and Dynamic Features of (Chloro)zirconocene Cations Stabilised by Pendant (Diarylphosphanyl)alkyl and (Dimethylamino)alkyl Substituents at Their Cyclopentadienyl Ring SystemsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 8 2003Steve Döring Abstract Treatment of the substituted (diarylphosphanyl)methyl group-4 metallocene complexes [(C5H4,CR1R2,PAr2)2ZrCl2] (2: R1/R2 = CH3/CH3, H/CH3, H/aryl) with Li[B(C6F5)4] in dichloromethane solution results in chloride ligand abstraction (with LiCl precipitation) to yield the complexes [(C5H4,CR1R2,PAr2)2Zr,Cl+] (5), with both phosphanyl groups internally coordinated to the metal centre. Three possible diastereoisomers are observed in the case of 5c (R1 = H; R2 = CH3), while bulkier R2 substituents give higher selectivities. The thermally induced (reversible) cleavage of the Zr,phosphane linkage results in dynamic NMR behaviour. Gibbs activation energies of ,G,(298 K) = 14.8 ± 0.5 and 14.5 ± 0.5 kcal/mol were obtained for these intramolecular equilibration processes in the complexes trans - 5d (R1 = H; R2 = Ph) and trans - 5e (R1 = H; R2 = ferrocenyl), respectively. Treatment of the substituted (dimethylamino)methyl metallocene complexes [(C5H4,CR1R2,NMe2)2ZrCl2] (6a, 6b) with Li[B(C6F5)4] proceeds analogously to yield the cation systems [{C5H4,C(CH3)2,NMe2}2ZrCl+] (12a) and [{C5H4,CH(CH3),NMe2}2ZrCl+] (12b, three possible diastereoisomers). Both complexes have their pairs of amino groups coordinated to the metal centre. The complexes exhibit dynamic NMR spectra. Selective equilibration of the diastereotopic N(CH3)A(CH3)B resonances of complex 12a is observed [,G,(233 K) = 11.5 ± 0.2 kcal/mol], whereas the adjacent C(CH3)A(CH3)B methyl groups remain diastereotopic. The dynamic equilibration of the latter was observed at a markedly higher temperature [,G,(333 K) = 17.3 ± 0.2 kcal/mol]. Treatment of [{C5H4,C(CH3)2,NMe2}CpZrCl2] (10) with Li[B(C6F5)4] resulted in the formation of complex [{C5H4,C(CH3)2,NMe2}CpZr,Cl+] (11), which shows the internal ,N(CH3)A(CH)B equilibration proceeding with a markedly higher activation barrier [,G,(333 K) = 17.6 ± 0.2 kcal/mol] than in 12a, and a stereochemical memory effect indicative of solvent coordination to the metal centre of the resulting highly electrophilic chlorozirconocene cation intermediate. Complex 11 was characterised by an X-ray crystal structure analysis, which shows the internal Zr,amine coordination. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Synthesis and Reactivity of 23 - tert -Butyl- and 23 -Phenyltetraarylazuliporphyrins: an Analysis of the Effect of Bulky Substituents on Oxidative Ring Contractions to Benzocarbaporphyrins,EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 24 2007Jessica A. El-Beck Abstract 6- tert -Butyl- and 6-phenylazulene reacted with pyrrole and benzaldehyde in a molar ratio of 1:3:4 in the presence of BF3·Et2O in chloroform, followed by oxidation with DDQ, to give 23 -substituted tetraphenylazuliporphyrins in 15,20,% yield. Slightly higher yields of the related meso -tetrakis(4-chlorophenyl)azuliporphyrins were obtained using 4-chlorobenzaldehyde. The presence of an electron-donating tert -butyl substituent increased the diatropic character of the azuliporphyrin system as determined by the proton NMR chemical shifts for the internal CH resonance, while intermediary results were noted for 23 -phenylazuliporphyrins. Addition of TFA afforded dications with increased aromatic ring currents, but electron-donating substituents (tBu,>,Ph) again produced a larger upfield shift for the internal CH signal due to stabilization of the tropylium character that is required so that the system can attain carbaporphyrin-type aromaticity. The substituted azuliporphyrins reacted with nickel(II) acetate or palladium(II) acetate to give the corresponding organometallic derivatives. In addition, oxidations with tBuOOH and KOH afforded benzocarbaporphyrin products in approximately 50,% yield. The presence of tert -butyl or phenyl substituents did not block these oxidative ring contraction processes, and the rate of reaction was slightly increased compared to 23 -unsubstituted azuliporphyrins. The major products were 22 - tert -butyl or phenyl-substituted benzocarbaporphyrins and minor products with an additional formyl substituent were also isolated. These products are consistent with an initial nucleophilic addition occurring at the position adjacent to the R group on the azulene ring. Detailed mechanisms are proposed to explain these observations. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] The Effects of Fluorine and Chlorine Substituents across the Fjords of Bifluorenylidenes: Overcrowding and StereochemistryEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 22 2006Sergey Pogodin Abstract The bistricyclic aromatic enes (BAEs) (E)- and (Z)-1,1,-difluorobifluorenylidene, 1,8,1,,8,-tetrafluorobifluorenylidene, (E)- and (Z)-3,3,-difluorobifluorenylidene, 3,6,3,,6,-tetrafluorobifluorenylidene, and their chlorinated analogues were subjected to a DFT study of overcrowding in their fjord regions. The B3LYP hybrid functional was employed to calculate energies and geometries of the twisted conformations of these BAEs. The diastereomers E11,F2 and Z11,F2 have identical twist angles (, = 37.1°) and similar degrees of overcrowding, but differ in the degree and mode of pyramidalization, ,. In E11,F2, ,(C9) = +,(C9,) = 7.0° (syn -pyramidalization), while in Z11,F2, ,(C9) = ,,(C9,) = 1.0° (anti -pyramidalization). By contrast, in E11,Cl2 and Z11,Cl2, , = 40.6° and 42.7°, respectively. Introducing four halogen substituents results in higher twist angles: , = 40.3° in 181,8,F4 and 52.6° in 181,8,Cl4. Surprisingly, Z11,F2 is more stable than E11,F2 (,H298 = ,1.9 kJ/mol), whereas Z11,Cl2 is less stable than E11,Cl2 (,H298 = 2.2 kJ/mol). Both results are consistent with the experimental relative stabilities of these diastereomers. The unexpected stability of Z11,F2 is explained by a combination of steric and electronic effects. Calculations of Coulomb energies for point charge systems of atoms C, F, and H in the fjord regions shows stabilization of the (Z) diastereomer by ,45.5 kJ/mol. The dipole,dipole interactions in the fjord region destabilize Z11,F2 by 6.4 kJ/mol relative to E11,F2. Careful examination of the NMR spectra of E11,F2 and Z11,F2 shows, in the latter, evidence of long-range fluorine,fluorine coupling over seven bonds (11.4 Hz) and carbon,fluorine coupling over six bonds (4.8 Hz).(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] First Propargyl Azides Bearing Strong Acceptor Substituents and Their Effective Conversion into Allenyl Azides: Influence of the Electronic Effects of Substituents on the Reactivity of Propargyl Azides,,EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 17 2005Joseph Rodolph Fotsing Abstract We have succeeded in the synthesis of propargyl azides containing 1- or 3-phenylthio functionalities. The selective oxidation of their sulfur atoms to sulfoxides and sulfones allows access to the first propargyl azides bearing acceptor substituents. Interestingly, the prototropic rearrangement of the latter propargyl azides leads to the formation of allenyl azides with relatively high stabilities and with moderate to good yields. Propargyl azides containing phenylthio functionalities react in the presence of nucleophiles to afford the expected N -unsubstituted 1,2,3-triazoles via short-lived allenyl azides. These results are entirely different from those of the corresponding sulfoxides and sulfones, which react under the analogous conditions either to produce the corresponding bis(triazolo)pyrazine derivatives or to yield newly substituted vinyl azides. The latter compounds can successfully be used as starting material providing access to azirines. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Microbial Baeyer,Villiger Oxidation of Prochiral Polysubstituted Cyclohexanones by Recombinant Whole-Cells Expressing Two Bacterial MonooxygenasesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 5 2005Marko D. Mihovilovic Abstract The microbial Baeyer,Villiger oxidation of prochiral 3,5-dimethylcyclohexanones bearing various functionalities with recombinant E. coli cells overexpressing cyclohexanone monooxygenase from Acinetobacter sp. NCIMB 9871 and cyclopentanone monooxygenase from Comamonas sp. NCIMB 9872 has been investigated. A distinct difference in substrate specificity and stereoselectivity of the two enzymes was observed, and enantiocomplementary products were obtained in some cases. The biocatalytic systems enabled access to chiral lactones as valuable intermediates for the total synthesis of various natural compounds. Substituents with varying lipophilicity and hybridization have been prepared by a diastereoselective synthetic route and subsequently bio-transformed for the investigation of conformational and electronic effects on the biooxidation,. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] | ||||||||||||||||||||||||||||||||||||||||||||||