High structural control in metal-mediated synthesis of new functionalized diphosphines using diphosphinoketenimines as precursors

The diphosphinoketenimine ligand in the neutral complexes fac-[MnI(CO)(3){(PPh(2))(2)C=C=NR}] (1 a: R = Ph; 1 b: R = p-tolyl) undergoes nucleophilic attack by MeLi and nBuMgCl yielding, after hydrolysis, the diphosphinoenamine-containing complexes fac-[MnI(CO)(3){(PPh(2))(2)C=C(R')NHR}] (3 a,b: R' = Me; 4 a,b: R' = nBu). Complex 1 a reacts under the same conditions with H(2)C=C=CHMgBr to afford fac-[MnI(CO)(3){(PPh(2))(2)C=C(CH(2)CC[triple chemical bond]CH)NHR}] (5 a), which contains a terminal alkyne group on the alpha-carbon atom of the diphosphinoenamine ligand. The cationic complexes fac-[Mn(CO)(4){(PPh(2))(2)C=C=NR}](+) (6) react with H(2)C=C=CHMgBr to afford diphosphinomethanide derivatives bearing three different types of functional groups, depending upon the substituent on the nitrogen atom of the ketenimine: cumulene in fac-[Mn(CO)(4){(PPh(2))(2)C--C(CH=C=CH(2))=N-xylyl}] (7 d), internal alkyne in fac-[Mn(CO)(4){(PPh(2))(2)C--C(C[triple chemical bond]CCH(3))=NtBu}] (8), and quinoline in 9 (R = Ph), whose formation implies an unusual cyclization process. Protonation of 7 d, 8, and 9 with HBF(4) occurs at the nitrogen atom to give the cationic derivatives 10 d, 11, and 12, respectively, which contain the corresponding functionalized diphosphine ligands. Irradiation of 3 a,b and 4 a,b with Vis/UV light makes it possible to isolate the free ligands (PPh(2))(2)C=C(R')NHR (13 a,b and 14 a,b), completing the metal-assisted synthesis of these novel functionalized diphosphines. Irradiation of 12 with Vis/UV light generates free phosphinoquinoline ligand 15, which readily affords a complex 16 containing 15 as a P,N-chelating ligand when treated with [PdCl(2)(NCMe)(2)], thus demonstrating its coordination capability.     

Photodissociation of propargyl chloride at 193 nm

The photodissociation of propargyl chloride (C3H3Cl) has been studied at 193 nm. Ion imaging experiments with state-selective detection of the Cl atoms and single-photon ionization of the C3H3 radicals were performed, along with measurements of the Cl + C3H3 and HCl + C3H2 recoil kinetic energy distributions, using a scattering apparatus with electron bombardment ionization detection to resolve the competing Cl and HCl elimination channels. The experiments allow the determination of the Cl (2P3/2) and Cl (2P1/2) (hereafter Cl) branching fractions associated with the C-Cl bond fission, which are determined to be 0.5 +/- 0.1 for both channels. Although prior translational spectroscopy studies by others had concluded that the low velocity signal at the Cl+ mass was due to daughter fragments of the HCl elimination products, the present work shows that Cl atoms are produced with a bimodal recoil kinetic energy distribution. The major C-Cl bond fission channel, with a narrow recoil kinetic energy distribution peaking near 40 kcal/mol, produces both Cl and Cl, whereas the minor (5%) channel, partitioning much less energy to relative kinetic energy, produces only ground spin-orbit state Cl atoms. The maximum internal energy of the radicals produced in the low-recoil-kinetic-energy channel is consistent with this channel producing electronically excited propargyl radicals. Finally, in contrast to previous studies, the present work determines the HCl recoil kinetic energy distribution and identifies the possible contribution to this spectrum from propargyl radicals cracking to C3+ ions in the mass spectrometer.     

New efficient approach for the synthesis of 2‐alkyl(aryl) substituted 4H‐pyrido[1,2‐a]pyrimidin‐4‐ones

A new, efficient and easy route for the preparation of a series of 2‐alkyl(aryl) substituted 4‐oxo‐4H‐pyrido‐[1,2‐a]pyrimidines, where alkyl = CH₃; aryl = C₆H₅, 4‐FC₆H₄, 4‐ClC₆H₄, 4‐BrC₆H₄, 4‐CH₃C₆H₄, 4‐OCH₃C₆H₄, 4‐NO₂C₆H₄ in 45–80 % yield from the reaction of β‐alkoxyvinyl trichloromethyl ketones with 2‐aminopyridine under mild conditions, is then reported.     

Molecular recognition: improved binding of biotin derivatives with synthetic receptors

NMR titrations and Monte Carlo conformational searches have been used to study the molecular recognition features of five urea derivatives with two synthetic hosts. We have improved the binding constant (Kb) values for all the studied guests and measured the largest binding constant of a complex involving a biotin derivative (biotin methyl ester) bound to a synthetic host by means of several interaction points and not only through the urea moiety.     

Convergent approaches for the synthesis of the antitumoral peptide, Kahalalide F. Study of orthogonal protecting groups

Kahalalide compounds are peptides that are isolated from a Hawaiian herbivorous marine species of mollusc, Elysia rufescens, and its diet, the green alga Bryopsis sp. Kahalalide F and its synthetic analogues are the most promising compounds of the Kahalalide family because they show antitumoral activity. Linear solid-phase syntheses of Kahalalide F have been reported. Here we describe several new improved synthetic routes based on convergent approaches with distinct orthogonal protection schemes for the preparation of Kahaladide analogues. These strategies allow a better control and characterization of the intermediates because more reactions are performed in solution.     

IB-01212, a new cytotoxic cyclodepsipeptide isolated from the marine fungus Clonostachys sp. ESNA-A009

IB-01212, a new cytotoxic cyclodepsipeptide featuring C2 symmetry, was isolated from the mycelium extract of Clonostachys sp. ESNA-A009. The amino acid sequence of the compound was determined by spectroscopy techniques. The absolute configuration of the amino acids was determined by a combination of the Marfey and menthol methods. The structure, which was confirmed by comparison of the analytical data for the natural product with a sample obtained by solid-phase peptide synthesis, was revealed to be a cyclic dimer formed by two chains of L-N,N-Me2Leu-L-Ser-L-N-MeLeu-L-N-MePhe bound by the two esters formed between the carboxylic acid of the L-N-MePhe and the hydroxyl function of the L-Ser. IB-01212 is highly cytotoxic to different tumor cell lines.     

Organocatalysis "on water". Regioselective [3 + 2]-cycloaddition of nitrones and allenolates

The first example of a regioselective and organocatalyzed 1,3-dipolar cycloaddition reaction between conjugated alkynoates and nitrones "on water" is described.     

Host-guest chemistry of tolbutamide

The molecular recognition features of tolbutamide with four synthetic hosts have been studied by means of NMR titrations, NOESY experiments and Monte Carlo (MC) conformational search. The interaction strength and the most probable structure reveal new insights on the recognition phenomena of this urea derivative in comparison with close related compounds.     

P-derived organic cations as structure-directing agents: synthesis of a high-silica zeolite (ITQ-27) with a two-dimensional 12-ring channel system

Recently, efforts have been made to synthesize large-pore, multidimensional zeolite frameworks as a basis for new catalysts to improve various hydrocarbon conversions. A new aluminosilicate zeolite, ITQ-27, has been prepared using the phosphorus-containing structure-directing agent, dimethyldiphenylphosphonium. Its crystal structure was determined in its calcined form by direct methods (FOCUS) on synchrotron powder diffraction data (lambda = 0.8702 A) after the unit cell and space group were determined from tilt electron diffraction experiments on individual microcrystals. The material crystallizes in space group Fmmm, where a = 27.7508(5) A, b = 25.2969(7) A, and c = 13.7923(4) A. The final model, refined by Rietveld methods, comprises seven unique T-sites forming a framework with straight 12-MR channels that are connected by 14-MR openings between them. (Corresponding 12-ring pore dimension is 6.94 A x 6.20 A.) Since access from one 14-MR opening to the next is through the 12-MR channel, the structure is best described as a two-dimensional, 12-MR framework.