A New Preparation of 1,3,3‐Trimethylbicyclo[2.2.2]octan‐2,6‐dione,a Never Isolated Intermediate in a Total Synthesis of (+)‐Norpatchoulenol. Formal Total Synthesis of (±)‐Iso‐Norpatchoulenol

A new preparation and the isolation and spectroscopic characterization of 1,3,3‐trimethylbicyclo[2.2.2]octan‐2,6‐dione ( 3 ), a so far elusive key intermediate in the Liu–Ralitsch total synthesis of (+)‐norpatchoulenol ((+)‐ 1a ), is described. The preparation of 3 constitutes also a formal total synthesis of (±)‐iso‐norpatchoulenol ((±)‐ 1b ), since 3 is correlated to an intermediate in the Monti and co‐workers synthesis of (±)‐ 1b .     

Assembly of a supramolecular capsule on a molecular printboard

A molecular capsule based on ionic interactions between two oppositely charged calix[4]arenes, 1 and 2, was assembled both in solution and on a surface. In solution, the formation of the equimolar assembly 1.2 was studied by (1)H NMR, ESI-MS, and isothermal titration calorimetry, giving an association constant (K(a)) of 7.5 x 10(5) M(-1). A beta-cyclodextrin self-assembled monolayer (beta-CD SAM) on gold was used as a molecular printboard to anchor the tetraguanidinium calix[4]arene (2). The binding of tetrasulfonate calix[4]arene 1 was monitored by surface plasmon resonance spectroscopy. Rinsing of the surface with a high ionic strength aqueous solution allows the removal of the tetrasulfonate calix[4]arene (1), while by rinsing with 2-propanol it is possible to achieve the complete desorption of the tetraguanidinium calix[4]arene (2) from the beta-CD SAM. The K(a) for the capsule formation on a surface is 3.5 x 10(6) M(-1), thus comparing well with the K(a) determined in solution.     

Synthesis of trimethylammoniumphenylthio-substituted phthalocyanines with different pattern of substitution

The base-catalyzed cyclotetramerization of 3-, 4- and 4,5-dimethylaminophenylthio phthalonitriles with zinc(II)acetate afforded 1(4),8(11),15(18),22(25)- and 2(3),9(10),16(17),23(24)-tetrasubstituted and 2,3,9,10,16,17,23,24-octasubstituted Zn(II)phthalocyanines, respectively. The statistical mixed condensation of the same phthalonitriles with 1,2-dicyanobenzene gave the corresponding mono- and disubstituted derivatives. Methylation of such products afforded a series of cationic Zn(II)phthalocyanines with different pattern of substitution, with potential use as photodynamic agents in microbial infections.     

Synthesis and NMR characterization of 3,4′-dibutoxy-2,2′-bithiophene

3,4′-Dibromo-2,2′-bithiophene was converted, in high yield, into the corresponding dibutoxy derivative. The ¹H ¹³C and nmr data are discussed in comparison with those of 3,3′- and 4,4′-dibutoxy-2,2′-bithiophene in relation to regiochemistry.     

Total syntheses of hyacinthacine A2 and 7-deoxycasuarine by cycloaddition to a carbohydrate derived nitrone

Practical syntheses of nitrone 8 by two different approaches from sugars are reported. Its use as a versatile intermediate in highly selective 1,3-dipolar cycloaddition reactions constitutes the key step for novel total syntheses of hyacinthacine A₂ (3) and 7-deoxycasuarine (20) by simple transformations of a common isoxazolidine adduct.     

Atropisomerism in 1,5-bridged calix[8]arenes

[structure: see text] The first example of two discrete calix[8]arene conformational isomers, 2 and 2a, has been obtained by exhaustive benzylation of 1,5-tetramethylene-bridged calix[8]arene 1. It is demonstrated, with the aid of X-ray crystallography, that these atropisomers have two 3/4-cone halves oriented syn or anti with respect to the bridge/bridgeheads moiety. VT NMR studies indicate that the tert-butyl-through-the-annulus inversion is inhibited in 1, while groups larger than n-hexyl or benzyl are required for curtailing the O-through-the-annulus route.     

Low oxidation state ruthenium chemistry : IV. The reactions of M(CO)2(PPh3)3 complexes (M = Fe,Ru) and the hydrogenation and isomerization of alkenes catalyzed by RuL(CO)2(PPh3)2 (L = H2, PPh3)

The complexes M(CO)₂(PPh₃)₃ (I, M = Fe; II, M = Ru) readily react with H₂ at room temperature and atmospheric pressure to give cis-M(H)₂(CO)₂(PPh₃)₂ (III, M = Fe;IV,M = Ru). I reacts with O₂ to give an unstable compound in solution, in a type of reaction known to occur with II which leads to cis-Ru(O₂)(CO)₂(PPh₃)₂(V). Even compound IV reacts with O₂ to give V with displacement of H₂; this reaction has been shown to be reversible and this is the first case where the displacement of H₂ by O₂ and that of O₂ by H₂ at a metal center has been observed. III and IV are reduced to M(CO)₃(PPh₃)₂ by CO with displacement of H₂; Ru(CO)₃- (PPh₃)₂ is also formed by treatment of IV with CO₂, but under higher pressure. Compounds II and IV react with CH₂CHCN to give Ru(CH₂CHCN)(CO)₂- (PPh₃)₂(VI) which reacts with H₂ to reform the hydride IV.cis-Ru(H)₂(CO)₂(PPh₃)₂(IV) has been studied as catalyst in the hydrogenation and isomerization of a series of monoenes and dienes. The catalysts are poisoned by the presence of free triphenylphosphine. On the other hand the ready exchange of H₂ and O₂ on the “Ru(CO)₂(PPh₃)₂” moiety makes IV a catalyst not irreversibly poisoned by the presence of air. It has been found that even Ru(CO)₂(PPh₃)₃(II) acts as a catalyst for the isomerization of hex-1-ene at room temperature under an inert atmosphere.     

Hydration process of cement in the presence of a cellulosic additive. A calorimetric investigation

In the cement industry, the extrusion technique is used to produce flat shapes with improved resistance to compression. Extrusion is a plastic-forming process that consists of forcing a highly viscous plastic mixture through a shaped die. The material should be fluid enough to be mixed and to pass through the die, and on the other hand, the extruded specimen should be stiff enough to be handled without changing in shape or cracking. These characteristics are industrially obtained by adding cellulosic polymers to the mixture. The aim of this work is to understand the action mechanism of these additives on the major pure phases constituting a typical Portland cement: tricalcium silicate (C(3)S), dicalcium silicate (C(2)S), tricalcium aluminate (C(3)A), and tetracalcium iron-aluminate (C(4)AF). In particular, a methylhydroxyethyl cellulose (MHEC) was selected from the best-performing polymers for further study. The effect of this additive on the hydration kinetics (rate constants, activation energies, and diffusional constants) was evaluated by means of differential scanning calorimetry (DSC) while the hydration products were studied by using thermogravimetry-differential thermal analysis (TG-DTA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). MHEC addition in calcium silicate pastes produces an increase in the induction time without affecting the nucleation-and-growth period. A less dense CSH gel was deduced from the diffusional constants in the presence of MHEC. Moreover, CSH laminar features and poorly structured hydrates were noted during the first hours of hydration. In the case of the aluminous phases, the additive inhibits the growth of stable cubic hydrated phases (C(3)AH(6)), with the advantage of the metastable hexagonal phases being formed in the earliest minutes of hydration.     

Synthesis and reactivity of 2-(porphyrin-2-yl)-1,3-dicarbonyl compounds

A simple and efficient procedure for the synthesis of porphyrins bearing 1,3-dicarbonyl moieties at the β-position is described. The new compounds were further functionalized and new derivatives containing an heterocyclic ring, an ethyl acetate residue or a 2-oxopropyl group at the β-position have been obtained.     

Geminate rebinding in R-state hemoglobin: kinetic and computational evidence for multiple hydrophobic pockets

Biphasic geminate rebinding of CO to myoglobin upon flash photolysis has been associated to ligand distribution in hydrophobic cavities, structurally detected by time-resolved crystallography, xenon occupancy, and molecular simulations. We show that the time course of CO rebinding to human hemoglobin also exhibits a biphasic geminate rebinding when the protein is entrapped in wet nanoporous silica gel. A simple branched kinetic scheme, involving the bound state A, the primary docking site C, and a secondary binding site B was used to calculate the microscopic rates and the time-dependent population of the intermediate species. The activation enthalpies of the associated transitions were determined in the absence and presence of 80% glycerol. Potential hydrophobic docking cavities within the alpha and beta chains of hemoglobin were identified by computational modeling using xenon as a probe. A hydrophobic pocket on the distal side of the heme, corresponding to Xe4 in Mb, and a nearby site that does not have a correspondence in Mb were detected. Neither potential xenon sites on the proximal side nor a migration channel from the distal to proximal site was located. The small enthalpic barriers between states B and C are in very good agreement with the location of the xenon sites on the distal side. Furthermore, the connection between the two xenon sites is relatively open, explaining why the decreased mobility of the protein with viscosity only slightly perturbs the energetics of ligand migration between the two sites.