Imine- and Amine-Type Macrocycles Derived from Chiral Diamines and Aromatic Dialdehydes

The condensation of aromatic dialdehydes with chiral diamines, such as 1,2-trans-diaminocyclohexane, leads to various enantiopure or meso-type macrocyclic Schiff bases, including [2 + 2], [3 + 3], [4 + 4], [6 + 6] and [8 + 8] condensation products. Unlike most cases of macrocycle synthesis, the [3 + 3] macrocycles of this type are sometimes obtained in high yields by direct condensation without a metal template. Macrocycles of other sizes from this family can often be selectively obtained in high yields by a suitable choice of metal template, solvent, or chirality of the building blocks. In particular, the application of a cadmium(II) template results in the expansion of the [2 + 2] macrocycles into giant [6 + 6] and [8 + 8] macrocycles. These imine macrocycles can be reduced to the corresponding macrocyclic amines which can act as hosts for the binding of multiple cations or multiple anions.     

A new procedure for the preparation of beta-keto-delta-lactones from sugars and their transformation into glycosyl acceptors in disaccharides synthesis

[reaction: see text] Glycals are effective starting materials for the synthesis of enantiopure beta-ketone-delta-lactones. They are easily transformed, through a two-step, one-pot reaction, into the corresponding alpha,alpha'-dioxothiones which in turn can be quantitatively trapped with dienophiles in inverse electron-demand [4 + 2] cycloadditions. The reaction of dioxothione 8b with endo and exo glucals allowed the elaboration of a new protocol to prepare 2-thio- or 2-deoxydisaccharides stereoselectively.     

2,6,9-Trioxabicyclo[3.3.1]nona-3,7-dien-4-oyl and tetraoxaadamantan-9-oyl functionalized aromatic di- and triamines: synthesis, stereochemistry and complexation

Primary amino groups of di- or triaminoaryl compounds add a remarkably stable dioxinyl-α-oxoketene affording bis- or tris-[trioxabicyclo[3.3.1]nona-3,7-dienyl (bridged bisdioxine)] systems which can be converted into the corresponding bis- or tris-[2,4,6,8-tetraoxadamantanes] by acidic hydrolysis. Stereochemical peculiarities as well as preliminary host-guest abilities of these molecules are investigated with aid of NMR-spectroscopy, an X-ray analysis and ESI-mass spectrometry.     

Understanding the nature of the molecular mechanisms associated with the competitive Lewis acid catalyzed [4+2] and [4+3] cycloadditions between arylidenoxazolone systems and cyclopentadiene: a DFT analysis

The molecular mechanisms of the reactions between aryliden-5(4H)-oxazolone 1, and cyclopentadiene (Cp), in presence of Lewis acid (LA) catalyst to obtain the corresponding [4+2] and [4+3] cycloadducts are examined through density functional theory (DFT) calculations at the B3LYP/6-31G* level. The activation effect of LA catalyst can be reached by two ways, that is, interaction of LA either with carbonyl or carboxyl oxygen atoms of 1 to render [4+2] or [4+3] cycloadducts. The endo and exo [4+2] cycloadducts are formed through a highly asynchronous concerted mechanism associated to a Michael-type addition of Cp to the beta-conjugated position of alpha,beta-unsaturated carbonyl framework of 1. Coordination of LA catalyst to the carboxyl oxygen yields a highly functionalized compound, 3, through a domino reaction. For this process, the first reaction is a stepwise [4+3] cycloaddition which is initiated by a Friedel-Crafts-type addition of the electrophilically activated carbonyl group of 1 to Cp and subsequent cyclization of the corresponding zwitterionic intermediate to yield the corresponding [4+3] cycloadduct. The next rearrangement is the nucleophilic trapping of this cycloadduct by a second molecule of Cp to yield the final adduct 3. A new reaction pathway for the [4+3] cycloadditions emerges from the present study.     

Synthesis of Ethyl 2-Cyano-3-Methylthio-3'-Arylaminoacrylate From Low Nucleophilic Amine

The synthesis of ketene N,S-acetals has attracted a considerable attention as building blocks in organic synthesis, especially in the preparation of heterocycles^[1]. The addition reaction of ketene S,S-acetals with highly nucleophilic amines, such as alkylamines, can easily afford the corresponding ketene N,S-acetals, under gentle condition, which could be converted into conjugated ketene aminals by reaction with a second equivalent of the same or a different amine^[2,3]. However, this addition reaction with low nucleophilic amines, such as arylamine or heterocyclic amine, can hardly give the corresponding ketene N,S-acetals under gentle conditions. If under powerful condition,such as refluxing, the addition reaction affords a mixture of the N,S-acetals and conjugated ketene aminals^[4]. Recent studies showed that this addition reaction with low nucleophilic amines affords the corresponding ketene N,S-acetals in the presence of a catalyst^[5].     

TEMPO-catalyzed aerobic oxidation of alcohols to aldehydes and ketones in ionic liquid [bmim][PF6

[reaction: see text]. A simple and mild TEMPO-CuCl catalyzed aerobic oxidation of primary and secondary alcohols to the corresponding aldehydes and ketones in ionic liquid [bmim][PF6] with no trace of overoxidation to carboxylic acids has been developed. The product can be isolated by a simple extraction with organic solvent, and the ionic liquid can be recycled or reused.     

Synthesis of nitrogen-containing heterocycles. 5. A new route to 5-amino-[1,2,4]triazolo[1,5-a][1,3,5]triazine derivatives

Treatment of certain diaminomethylenehydrazones 1 of aromatic carbonyl compounds with ethyl N-cyanoimidate ( 2 ) in acetonitrile in the presence of a tertiary amine at room temperature gives the corresponding amino(N-cyanoiminomethyl)aminomethylenehydrazones 3 in high yields. The intermediate 3 can readily be cyclized to the corresponding 5-amino-2,3-dihydro[1,2,4]triazolo[1,5-a][1,3,5]triazines 4 in moderate to good yields by brief heating in acetonitrile. When the reaction of diaminomethylenehydrazones 1 with ethyl N-cyanoimidate ( 2 ) is performed at reflux temperature in the presence of a tertiary amine, 5-amino-2,3-dihydro[1,2,4]triazolo[1,5-a]1,3,5]triazines 4 can be directly obtained in moderate yields. The yields of triazolotriazine produced by the one-step synthesis are generally comparable or even higher than the overall yields from the two-step procedure.     

1,7-Asymmetric induction in a nitrogen ring expansion process facilitated by in situ tethering

[formula: see text] There are only a few methods for the asymmetric ring expansion of prochiral ketones. Symmetrically substituted cyclohexanones can be converted to the corresponding ring-expanded caprolactam with excellent 1,7-diastereoselectivity (> or = 93% ds) and yields (> or = 86%), using a chiral hydroxy azide-mediated Schmidt reaction.     

Formation of N‐Heterocyclic Carbenes by Tautomerization of Mesomeric Betaines: Cyclic Boron Adducts and Palladium Complexes From 2‐(Imidazolium‐1‐yl)phenolates

2‐(Imidazolium‐1‐yl)phenolates are conjugated heterocyclic mesomeric betaines in tautomeric equilibrium with the corresponding N‐heterocyclic carbenes (NHCs), 3‐(2‐hydroxyphenyl)‐imidazol‐2‐ylidenes. The carbene tautomers can be trapped as thiones (X‐ray analysis). Moreover, bis(triphenylphosphine)palladium(II) dichloride in THF trapped the carbene tautomer as a palladium complex without participation of the phenolate group (X‐ray analysis). The corresponding anionic NHCs, 2‐phenolate‐substituted imidazol‐2‐ylidenes, can be trapped by triethylborane or triphenylborane to form 4,4‐diethyl‐ or 4,4‐diphenyl‐4H‐benzo[e]imidazo[2,1‐c][1,4,2]oxaza‐borininium‐4‐ides, respectively (two X‐ray analyses). These tricyclic systems are the first representatives of a new heterocyclic ring system. The results of DFT calculations concerning the HOMO/LUMO profiles and partial charges are also presented.     

Synthesis of oxazines and N-arylpyrroles by reaction of unfunctionalized dienes with nitroarenes and carbon monoxide,catalyzed by palladium-phenanthroline complexes

The reaction between an unfunctionalized conjugated diene and a nitroarene under CO pressure and at 100 degrees C, catalyzed by [Pd(Phen)2][BF4]2 (Phen = 1,10-phenanthroline), affords the corresponding hetero-Diels-Alder adduct (oxazine) in up to 91% yields in one pot. If the reaction mixture is then heated to 200 degrees C, the oxazines are converted into the corresponding N-arylpyrroles in good yields. Pressures as low as 5 bar can be employed, and 0.08% catalyst is sufficient to effect the transformation. The reaction can be equally run by employing the nitroarene or the diene as limiting agent and works well for nitroarenes bearing either electron-withdrawing or mildly electron-donating substituents. A moderate steric hindrance on the nitroarene (o-methyl) is well tolerated, but 1,4-disubstituted-1,3-dienes are not suitable substrates.     

Conversion of N-aromatic amides to O-aromatic esters

[reaction: see text] N-Aromatic secondary amides can be transformed into O-aromatic esters in high yield via N-nitrosamide intermediates. The amides can be generated in situ from the corresponding aromatic amines or nitro compounds, and phenols can easily be made from the esters. The reaction can be modified by addition of methyl methacrylate or toluene at 0 degrees C to give polymerization or deamination, respectively. The rearrangement mechanism may involve radical formation and recombination.     

Novel Synthesis of 1,8-Alkanopyrido[3,4-d]pyridazine: a New Ring System

Cycloalkylidenemalononitriles couple with various diazonium salts to yield the corresponding cycloalkeno[c]pyridazines, which react with trichloroacetonitrile to give the 1,8-alkanopyrido[3,4-d]pyridazines. The reaction of cycloalkenopyridazines with DMF dimethylacetal gives enamine derivatives, which can be converted to 1,8-alkanopyrido[3,4-d]pyridazines via treating with hydrazine hydrate or aromatic amines. Substituted cycloalkenopyridines react with diazoaminobenzene to afford the corresponding 1,8-alkanopyridopyridazines.     

The chemistry of indole

A number of amides of indole ketoacids are synthesized. 3-Carboxyacylindoles can be converted to the corresponding enol-lactones by treatment with acetic anhydride or acetyl chloride. Reaction of the lactones with ammonia or amines involves lactone ring opening, and this makes it possible to prepare some N-substituted or unsubstituted ketoacid amides. Deacylation can occur in the action of strong bases or high temperatures on indoleketoacids. Reaction of 2-(indolyl-3') benzoic acid with dimethyl sulfate proceeds in two ways: the NH group is methylated, and there is conversion to the corresponding indolenine, with subsequent methylation of the enol.For Part II see [1].     

Silicon-initiated carbonylative carbotricyclization and [2+2+2+1] cycloaddition of enediynes catalyzed by rhodium complexes

The reaction of dodec-11-ene-1,6-diynes or their heteroatom congeners with a hydrosilane catalyzed by Rh(acac)(CO)2 at ambient temperature and pressure of CO gives the corresponding fused 5-7-5 tricyclic products, 5-oxo-1,3a,4,5,7,9-hexahydro-3H-cyclopenta[e]azulenes or their heteroatom congeners, in excellent yields through a unique silicon-initiated cascade carbonylative carbotricyclization (CO-SiCaT) process. It has also been found that the 5-7-5 fused tricyclic products can be obtained from the same type of enediynes and CO through a novel intramolecular [2+2+2+1] cycloaddition process. The characteristics of these two tricyclization processes and the fundamental differences in their reaction mechanisms are discussed. This novel higher-order cycloaddition reaction has also been successfully applied to the tricyclization of undeca-5,10-diyn-1-als, affording the corresponding 5-7-5 fused-ring products bearing a seven-membered lactone moiety. Related [2+2+2] tricyclizations of enediyne and diynal substrates are also discussed. These newly discovered reactions can construct multiple bonds all at once, converting linear starting materials to polycyclic compounds in a single step. Thus, these new processes provide innovative routes to functionalized polycyclic compounds that are useful for the syntheses of natural and unnatural products.     

Electron ionization and electrospray mass spectra of diaryl-substituted enaminoketones and their thio analogs

Electron ionization (EI) and positive electrospray ionization (ESI) mass spectra of selected diaryl enaminoketones and enaminothiones have been studied. In the EI mass spectra of both classes of compound, molecular ion peaks are accompanied by the peaks corresponding to the [M-H](+) ions. The formation of these ions can be rationalized by a cyclization reaction resulting in the formation of the respective isoxazolium and isothiazolium cations. Under positive ESI conditions, in the spectra recorded for the enaminoketones peaks corresponding to the [M+H](+), [M+Na](+) and [2M+Na](+) ions appeared, while in the spectra recorded for the enaminothiones, peaks corresponding to the [M-H](+) ions were dominant. These ions are most likely formed by oxidation of the neutral enaminothione molecules on the surface of the positively charged stainless steel capillary in the ESI ion source (anodic oxidation).     

How to Bend a Cumulene

Allenes (carbodicarbenes) and [3]cumulenes are linear carbon chains that can be bent when the terminal group has a strong carbene nature. This bending can be quite pronounced in allenes but not in [3]cumulenes. In this study, how N-heterocyclic or cyclic (alkyl)(amino) carbene (NHC and CAAC, respectively) terminal groups can modify the linear structure of [n]cumulenes has been analyzed. A low π acidity of the terminal carbene affects the linearity of [2n]cumulenes. Indeed, it has been found that the NHC [4]cumulene is extremely bent, contrary to classical [4]cumulenes. The predicted NHC [4]cumulene or tricarbodicarbene has two lone pairs and the π electrons are delocalized over the whole molecule. More significantly, DFT calculations have shown that this bent [4]cumulene is very stable, considerably more so than the corresponding [3]cumulene, which has been elusive to synthesize. Remarkably, calculations have shown that all the NHC [2n]cumulenes are more than 25 kcal mol⁻¹ more stable than the [2n−1]cumulenes.     

On the critical temperature, normal boiling point, and vapor pressure of ionic liquids

One-stage, reduced-pressure distillations at moderate temperature of 1-decyl- and 1-dodecyl-3-methylimidazolium bistriflilamide ([Ntf(2)](-)) ionic liquids (ILs) have been performed. These liquid-vapor equilibria can be understood in light of predictions for normal boiling points of ILs. The predictions are based on experimental surface tension and density data, which are used to estimate the critical points of several ILs and their corresponding normal boiling temperatures. In contrast to the situation found for relatively unstable ILs at high-temperature such as those containing [BF(4)](-) or [PF(6)](-) anions, [Ntf(2)](-)-based ILs constitute a promising class in which reliable, accurate vapor pressure measurements can in principle be performed. This property is paramount for assisting in the development and testing of accurate molecular models.     

Synthesis of hexahomotrioxacalix[3]naphtalenes and a study of their alkali-metal cation binding properties

The first syntheses of the C3-symmetrical and unsymmetrical hexahomotrioxacalix[3]naphthalenes 3 and 4, respectively, and the corresponding tert-butyl hexahomotrioxacalix[3]naphthalene 3a are reported. A convergent synthesis of the linear hexahomotrimer precursors 19 and 19a is described, but the direct synthesis of 3 and 3a can also be achieved from the monomers 20 and 20a, respectively. A limited study of the binding properties of alkali-metal cations by 3 or 3a using a picrate-CHCl3 extraction showed only weak abilities to bind with the cations examined.     

Synthesis of iridium pyridinyl N-heterocyclic carbene complexes and their catalytic activities on reduction of nitroarenes

Coordination of iridium(I) metal ions with a pyridinyl imidazol-2-ylidene ligand (pyNwedgeC-R) [R=Me, mesityl(2,4,6-trimethylphenyl)] that processes bulky substituents has been investigated. The iridium carbene complexes [(C-pyNwedgeC-R)IrCl(COD)] (COD=1,5-cyclooctadiene) are prepared via transmetalation from the corresponding silver carbene complexes. Upon the abstraction of chloride, the chelation of pyNwedgeC becomes feasible, resulting in the formation of [C,N-(pyNwedgeC-R)Ir(COD)](BF4) (4). The coordinated COD of complex 4 can be replaced by carbon monoxide to yield the corresponding carbonyl species [C,N-(pyNwedgeC-R)Ir(CO)2](BF4). The labile nature of the pyridinyl nitrogen donor is readily replaced by acetonitrile, as is evidenced by the NMR study. All iridium complexes show catalytic activity on the hydrogen-transfer reduction of carbonyl and nitro functionalities. By manipulation of the reaction conditions, the iridium-catalyzed reduction of nitroarenes can selectively provide aniline or azo compounds as the desired product.     

Nicotine: on the potential role of ionic liquids for its processing and purification

Marked solubility differences of nicotine in the ionic liquids [C(2)mim][NTf(2)], [C(2)mim][EtOSO(3)], and [C(n)mim]Cl, 6 相似文献