Tetradecanol dehydrogenation over CuO catalyst supported on BaO, CaO and MgO

Bimetallic Cu/Mg, Ca, Ba mixed oxide compounds acted as catalyst in the dehydrogenation of tetradecanol into tetradecanal, and were characterized by thermal gravimetric analysis, surface area, X-ray diffraction, temperature-programmed reduction and desorption of CO₂. Alkaline earth oxides increased the total basic site concentration in the order of Mg>Ca>Ba. A correlation was found between the total basic site concentration and initial dehydrogenation rate. This revised version was published online in June 2006 with corrections to the Cover Date.     

An electrolytic device for preparation of hydrogen and oxygen from water for isotopic analysis

An electrolytic device for decomposition of water has been developed which readily gives hydrogen and oxygen for isotopic measurement with a mass spectrometer. A 20-mul sample can be decomposed quantitatively in 10 min with good reproducibility. The results produced are comparable with those obtained by reduction with uranium.     

Microbial Transformation of Sesquiterpenes, (−)‐Ambrox® and (+)‐Sclareolide

The microbial transformation of (?)‐Ambrox^® ( 1 ), a perfumery sesquiterpene, by a number of fungi, by means of standard two‐stage‐fermentation technique, afforded ambrox‐1α‐ol ( 2 ), ambrox‐1α,11α‐diol ( 3 ), ambrox‐1α,6α‐diol ( 4 ), ambrox‐1α,6α,11α‐triol ( 5 ), ambrox‐3‐one ( 6 ), ambrox‐3β‐ol ( 7 ), ambrox‐3β,6β‐diol ( 8 ), 13,14,15,16‐tetranorlabdane‐3,8,12‐triol ( 9 ), and sclareolide ( 10 ) (Schemes 1 and 2). Further incubation of compound 10 with Cunninghamella elegans afforded 3‐oxosclareolide ( 11 ), 3β‐hydroxysclareolide ( 12 ), 2α‐hydroxysclareolide ( 13 ), 2α,3β‐dihydroxysclareolide ( 14 ), 1α,3β‐dihydroxysclareolide ( 15 ), and 3β‐hydroxy‐8‐episclareolide ( 16 ) (Scheme 3). Metabolites 2 – 5, 12, 13 , and 16 were found to be new compounds. The major transformations include a reaction path involving hydroxylation, ether‐bond cleavage and inversion of configuration. Metabolites 11 – 16 of sclareolide showed significant phytotoxicity (Table 1). The structures of the metabolites were characterized on the basis of spectroscopic techniques.     

Synthesis of a novel cis-proline-derived cyclic type VI beta-turn mimic via ring-closing metathesis

A cis-proline derived cyclic mimic of a type VI beta-turn is synthesized via a ring-closing metathesis reaction. The solution NMR conformational study indicates that the major conformer of the cyclic peptide adopts a type VIa beta-turn in CDCl(3) and a type VIb beta-turn in DMSO-d(6).     

Use of tetrahydropyrimidinium salts for highly efficient palladium-catalyzed cross-coupling reactions of aryl bromides and chlorides

New, sterically demanding 1,3-dialkyl-3,4,5,6-tetrahydropyrimidinium salts (2) as NHC precursors have been synthesized and characterized. These salts, in combination with palladium acetate, provided active catalysts for the cross-coupling of aryl chlorides and bromides under mild conditions. The catalytic system was applied to the Heck, Suzuki and benzaldehyde (Kumada) coupling reactions. Catalyst activity was found to be influenced by the presence of a methoxy group on the ring of the p-position of benzyl substituent of the ligand precursor.     

Palladium(0)-catalyzed regioselective synthesis of alpha-dehydro-beta-amino esters from amines and allyl acetates: synthesis of a alpha-dehydro-beta-amino acid derived cyclic peptide as a constrained beta-turn mimic

Acetates derived from the adducts of the Baylis-Hillman reaction can be reacted in a regioselective manner with amines in the presence of palladium(0) catalyst to afford alpha-dehydro-beta-amino esters (2 and 3) in good yields. The regioselectivity of the reaction can be controlled by temperature and reaction medium leading to the synthesis of regioisomers 2 or 3. The alpha-dehydro-beta-amino acid 3 is a turn inducer, and the dipeptides 6 derived from it show the presence of an eight-membered intramolecular hydrogen bond. Also, cobalt(II) chloride catalyzes the cleavage of epoxy peptides with alpha-dehydro-beta-amino acid derivative 3b to afford the corresponding dipeptide derivatives 8, which exhibit an intramolecular hydrogen bond and thus mimic a beta-turn. This intramolecular hydrogen bonding preorganizes the corresponding diallylated peptide 8c for cyclization via ring-closing metathesis to afford the cyclic peptide 9 as a constrained mimic of a beta-turn.     

Reverse turn induced pi-facial selectivity during polyaniline-supported cobalt(II) salen catalyzed aerobic epoxidation of N-cinnamoyl L-proline derived peptides

A novel chemo- and diastereoselective aerobic epoxidation of the N-cinnamoyl peptides catalyzed by polyaniline-supported cobalt(II) salen (PASCOS) is described. The N-cinnamoyl proline derived peptides 1 show a high pi-facial selectivity during these epoxidations. The origin of this diastereoselectivity in 1 has been attributed to (i) the propensity of the N-cinnamoyl proline amide to exist predominantly as trans rotamer in CDCl3, DMSO-d6, and CH3CN medium and (ii) existence of these peptides as organized structures (gamma- and beta-turns) due to the presence of intramolecular hydrogen bonds. An extensive solution NMR and MD simulation study on 1d and 1f indicates that the origin of the high pi-facial selectivity is due to the well-defined gamma- and beta-turns which result in the hindrance of one face of the cinnamoyl double bond in the transition state of the epoxidation reaction.     

A study of simultaneous photolysis and photoaddition reactions of riboflavin in aqueous solution

The photodegradation reactions of riboflavin (RF) in the presence of 0.05-2.00 M phosphate (pH 7.0) have been studied using a specific multicomponent spectrophotometric method. The reactions involve simultaneous photolysis (intramolecular photoreduction) and photoaddition (intramolecular photoaddition) leading to lumichrome (LC) and cyclodehydroriboflavin (CDRF), respectively, as major products. The contribution of each reaction in the overall photodegradation depends upon the phosphate concentration, i.e., higher the phosphate concentration higher the extent of photoaddition. The apparent first-order rate constants for the photodegradation of RF and for the formation of LC and CDRF at 0.25-2.00 M phosphate concentration range from 0.65 to 3.03 x 10(-2), and from 0.41 to 0.99 x 10(-2) and 0.12 to 1.63 x 10(-2) min(-1), respectively. The second-order rate constants for the phosphate catalysed photodegradation of RF and for the formation of LC and CDRF are 2.12 x 10(-4) and 0.61 x 10(-4) and 1.41 x 10(-4) M(-1)s (-1), respectively. Since the formation of CDRF by photoaddition is catalysed by HPO(4)(2-) ions, it is suggested that H(2)PO(4)(-) ions may be involved in the formation of LC by photolysis. Thus, both H(2)PO(4)(-) and HPO(4)(2-) ions may catalyse the two major reaction pathways of riboflavin photodegradation, respectively.     

The potential of serially coupled alkyl-bonded silica monolithic columns for high resolution separations of pharmaceutical compounds in biological fluids

Summary In this paper we investigate the potential of alkyl-bonded silica monolithic columns for the isolation and identification of drug-related components in biological fluids. Up to 6 columns have been connected in series to produce a chromatographic system with up to 40,000 plates. This high-resolution chromatography system has been coupled to both MS and NMR to enable efficient detection and characterisation of drug-related components in biological fluids. The use of six coupled columns has been shown to give enhanced resolution over a high quality silica particulate column packed with 3 μm material which exhibits the same back pressure. The effect of volume and mass load on the performance of monolithic columns for semi-preparative chromatography of biological fluids has also been investigated. In these studies it was possible to inject up to 100 mL of neat urine with no loss of chromatographic performance. Furthermore, upon re-testing, the columns showed similar chromatographic performance. Again several columns were serially connected, producing enhanced resolution in the semi-preparative mode.