笼形水簇和溶解甲烷之间平均力势能的约束型分子动力学计算及其在天然气水合物成核研究中的意义

That the dodecahedral water cluster (DWC) can adsorb dissolved methane molecules, an important phenomenon related to the hydrate nucleation study, has been observed through molecular dynamics simulations, but it has not been explained satisfactorily [Guang-Jun Guo; Yi-Gang Zhang; Hua Liu. J. Phys. Chem. C, 2007, 111, 2595]. In order to explain this phenomenon by using the potential of mean force (PMF) between the DWC and the dissolved methane, we perform several series of constrained molecular dynamics simulations in the methane-water system. The distance between the center of DWC and the methane molecule is constrained from 5 Å to 18 Å by adding 0.2 Å every time. For each fixed distance, we perform 20 independent simulations to improve the statistical precision. We first get the constraint force between the DWC and the dissolved methane in each simulation and then calculate the PMF by integrating these forces. Subsequently, the radial distribution function (RDF) is obtained from the PMF through an equation of statistical mechanics. The results show that the RDF has a sharp peak at about 6.2 Å, successfully explaining why the DWC adsorbs dissolved methane molecules. The preferential binding coefficient is a positive value (=2.05±0.5), indicates that the DWC tends to adsorb dissolved methane rather than water molecules in methane aqueous solutions. The curve of PMF for the DWC encaging a methane almost coincides that for the empty DWC, meaning that it is the DWC rather than the encaged methane who could adsorb dissolved methane molecules. By comparing the curves of PMF for different directions of the DWC relative to the dissolved methane, we find that it is the cage face rather than the cage edge or vertex that plays an essential role when the DWC adsorbing dissolved methane. This research sheds light on the driving force for the methane adsorption, and it is helpful in understanding the nucleation process of methane hydrate.

东海陆架盆地西南部烟囱构造与油气运聚关系研究

In recent years, chimney structure has been proved one of important indicators and a useful guide to major petroleum fields exploration through their exploration history both at home and abroad. Chimney structure, which has been called "gas chimney" or "seismic chimney", is the special fluid-filled fracture swarm, which results from the boiling of active thermal fluid caused by abruptly decreasing of high pressure and high temperature in sedimentary layers of upper lithosphere. Chimney structure is well developed in continental shelf basin of East China Sea, which indicates the great perspectives of petroleum resources there. However, the chimney structure also complicated the petroleum accumulation. So the study of chimney structure on its formation, its effect on occurrence and distribution of petroleum fields is very important not only on theoretical, but also on its applied research. It is for the first time to make a clear definition of chimney structure in this paper, and the existence and practical meaning of chimney structure are illustrated. Firstly, on the viewpoint of exploration, this will amplify exploration area or field, not only in marine, but also on continent. Secondly, this is very important to step-by-step exploration and development of petroleum fields with overpressure. Thirdly, this will provide reference for the study on complex petroleum system with multi-sources, commingled sources and accumulation, multi-stage accumulations, and multi-suits petroleum system in the overlay basin. Fourthly, when the thermal fluid enters the oceanic shallow layer, it can help form gas hydrate under favorable low-temperature and high-pressure conditions. Meanwhile, the thermal fluid with its particular component and thermal content will affect the physical, chemical and ecological environments, which will help solving the problem of global resources and environment. Beginning from the regional tectonic evolution characteristics, this paper discussed the tectonic evolution history of the Taibei depression, then made an dynamical analysis of the tectonic-sedimentary evolution during the Mesozoic and Cenozoic for the East China Sea basin. A numerical model of the tectonic-thermal evolution of the basin via the Basin-Mod technique was carried out and the subsidence-buried history and thermal history of the Taibei depression were inverse calculated: it had undergone a early rapid rift and sag, then three times of uplift and erosion, and finally depressed and been buried. The Taibei depression contains a huge thick clastic sedimentary rock of marine facies, transitional facies and continental facies on the complex basement of ante-Jurassic. It is a part of the back-arc rifting basins occurred during the Mesozoic and Cenozoic. The author analyzed the diagenesis and thermal fluid evolution of this area via the observation of cathodoluminescence, scanning electron microscope and thin section, taking advantage of the evidences of magma activities, paleo-geothermics and structural movement, the author concluded that there were at least three tectonic-thermal events and three epochs of thermal-fluid activities; and the three epochs of thermal-fluid activities were directly relative to the first two tectonic-thermal events and were controlled by the generation and expulsion of hydrocarbon in the source rock simultaneously. Based on these, this paper established the corresponding model between the tectonic-thermal events and the thermal-fluid evolution of the Taibei Depression, which becomes the base for the study on the chimney structures. According to the analyses of the gas-isotope, LAM spectrum component of fluid inclusion, geneses of CO_2 components and geneses of hydrocarbon gases, the author preliminarily verified four sources of the thermal fluid in the Taibei Depression: ① dehydration of mud shale compaction, ② expulsion of hydrocarbon in the source rock; ③ CO_2 gas hydro-thermal decomposition of carbonatite; ④magma-derived thermal fluid including the mantle magma water and volatile components (such as H_2O, CO_2, H_2S, SO_2, N_2 and He etc.). On the basis of the vitrinite reflectance (Ro), homogenization temperature of fluid inclusion, interval transit time of major well-logging, mud density of the wells, measured pressure data and the results of previous studies, this paper analyzed the characteristics of the geothermal fields and geo-pressure fields for the various parts in this area, and discussed the transversal distribution of fluid pressure. The Taibei depression on the whole underwent a temperature-loss process from hot basin to cold basin; and locally high thermal anomalies occurred on the regional background of moderate thermal structure. The seal was primarily formed during the middle and late Paleocene. The overpressured system was formed during the middle and late Eocene. The formation of overpressured system in Lishui Sag underwent such an evolutionary process as "form-weaken-strengthen-weaken". Namely, it was formed during the middle and late Eocene, then was weakened in the Oligocene, even partly broken, then strengthened after the Miocene, and finally weakened. The existence of the thermal fluid rich in volatile gas is a physical foundation for the boiling of the fluid, and sharply pressure depletion was the major cause for the boiling of the fluid, which suggests that there exists the condition for thermal fluid to boil. According to the results of the photoelastic simulation and similarity physical experiments, the geological condition and the formation mechanism of chimnestructures are summarized: well compartment is the prerequisite for chimney formation; the boiling of active thermal fluid is the original physical condition for chimney formation; The local place with low stress by tension fault is easy for chimney formation; The way that thermal fluid migrates is one of the important factors which control the types of chimney structures. Based on where the thermal fluid come from and geometrical characteristics of the chimney structures, this paper classified the genetic types of chimney structures, and concluded that there existed three types and six subtypes chimney structures: organic chimney structures generated by the hydrocarbon-bearing thermal fluid in middle-shallow layers, inorganic and commingling-genetic chimney structures generated by thermal fluid in middle-deep layers. According to the seismic profiles interpretations, well logging response analysis and mineralogical and petrological characteristics in the study area, the author summarized the comprehensive identification marks for chimney structures. Especially the horizon velocity analysis method that is established in this paper and takes advantage of interval velocity anomaly is a semi-quantitative and reliable method of chimney structure s identification. It was pointed out in this paper that the occurrence of the chimney structures in the Taibei depression made the mechanism of accumulation complicated. The author provided proof of episodic accumulation of hydrocarbon in this area: The organic component in the boiling inclusion is the trail of petroleum migration, showing the causality between the boiling of thermal fluid and the chimney structures, meanwhile showing the paroxysmal accumulation is an important petroleum accumulation model. Based on the evolutionary characteristics of various types of chimney structures, this paper discussed their relationships with the migration-accumulation of petroleum respectively. At the same time, the author summarized the accumulating-dynamical models associated with chimney structures. The author analyzed such accumulation mechanisms as the facies state, direction, power of petroleum migration, the conditions of trap, the accumulation, leakage and reservation of petroleum, and the distribution rule of petroleum. The author also provides explanation for such practical problems the existence of a lot of mantle-derived CO_2, and its heterogeneous distribution on plane. By study on and recognition for chimney structure, the existence and distribution of much mantle-derived CO_2 found in this area are explained. Caused by tectonic thermal activities, the deep magma with much CO_2-bearing thermal fluid migrate upward along deep fault and chimney structures, which makes two wells within relatively short distance different gas composition, such as in well LF-1 and well LS36-1-1. Meanwhile, the author predicted the distribution of petroleum accumulation belt in middle-shallow layer for this area, pointed out the three favorable exploration areas in future, and provided the scientific and deciding references for future study on the commingling-genetic accumulation of petroleum in middle-deep layer and the new energy-gas hydrate.

Preparation of lanthanide hydrides of nanometric size by the catalytic method

Rare-earth metals were hydrogenated in the presence of TiCl4 catalyst in tetrahydrofuran (THF) at 45 degreesC under normal pressure. Transmission electron micrographs showed that the re. sulting lanthanide hydrides were in the form of nanoparticles. The rate of hydrogenation decreased with increasing atomic number of the rare-earth elements.

Effects of organic modifiers on solute retention and electrokinetic migrations in micellar electrokinetic capillary chromatography

Influences of seven organic modifiers, including urea, methanol (MeOH), dioxane (DIO), tetrahydrofuran (THF), acetonitrile (ACN), 1-propanol (1-PrOH) and 2-propanol (2-PrOH), on the solute retention and the electrokinetic migrations in micellar electrokinetic capillary chromatography (MEKC) are investigated with sodium dodecyl sulfate (SDS) micelle as pseudostationary phase. It is observed that in the limited concentration ranges used in the MEKC systems the effect of organic modifier concentration on the retention can be described by the equation logk'=logk'(w)-SC for most binary aqueous-organic buffer, but deviations from this retention equation are observed at ACN and particularly THF as organic modifiers. With parameter S as a measure of the elutropic strength, the elutropic strength of the organic modifiers is found to follow a general order urea

Precursor chemistry for oxide related materials

This thesis describes modelling, synthesis, spectroscopic and physical characterisation, as well as application of Magnesium, Calcium and Copper β-diketonate, β-ketoiminate, β-diiminate, Schiff base, amide and fluorenyl compounds. The selected compounds could potentially find application in materials deposition using Atomic Layer Deposition (ALD), MOCVD, CVD and Sol-Gel techniques. Quantum chemical modelling was used as a tool to perform the comprehensive and rapid study of magnesium and calcium precursor molecules in order to predict which of them would be more successful in ALD of metal oxides. Precursor chemistry plays a key role in ALD, since precursors must be volatile, thermally stable, chemisorb on the surface and react rapidly with existing surface groups. This Thesis describes one aspect of this, surface reactivity between ligands and hydroxyl groups, via a gas-phase model with energetics computed at the level of Density Functional Theory (DFT). A number of different synthetic strategies, both aerobic and anaerobic, were investigated for the synthesis of the described metal complexes. These included the use of different metal starting reagents such as, anhydrous and hydrated inorganic metal salts, metal alkyls and Grignard reagents. Some of previously unreported metal complexes of homoleptic and heteroleptic magnesium, calcium and copper β-diketonates, β-ketoiminates, β-diiminates, amides and Schiff base type were synthesised and characterised: [Mg(hfpd)2(DipPa)], [Mg(hfpd)2(MapH)2], [Mg(hf-ebp)(THF)2], [Mg(tf-Pap)Cl(THF)2], [Ca(PhNacnac)2], [Cu(tf-Pap)2], [Cu(PhNacnac)2], [Cu(hf-ebp)], [Cu(DipPa)] and [Cu(DipPa)2(4,4’-bypy)]. A comprehensive study on the thermal properties of magnesium, calcium and copper β-diketonates, β-ketoiminates, β-diiminates, Schiff base, amide and fluorenyl complexes was performed using TGA and sublimation of selected compounds. Atomic Layer Deposition of MgO using magnesium β-ketoiminate – [bis{(4-N-phenyl)-2-pentonato} magnesium] and β-diketonate - [bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)(THF)magnesium hydrate] was performed on Si(100) substrates at 180°C and 0.2 Torr using O2 plasma.

Reductive elimination of hypersilyl halides from zinc (II) complexes. Implications for electropositive metal thin film growth

Treatment of Zn(Si(SiMe3)3)2 with ZnX2 (X = Cl, Br, I) in tetrahydrofuran (THF) at 23 °C afforded [Zn(Si(SiMe3)3)X(THF)]2 in 83–99% yield. X-ray crystal structures revealed dimeric structures with Zn2X2 cores. Thermogravimetric analyses of [Zn(Si(SiMe3)3)X(THF)]2 demonstrated a loss of coordinated THF between 50 and 155 °C and then single-step weight losses between 200 and 275 °C. The nonvolatile residue was zinc metal in all cases. Bulk thermolyses of [Zn(Si(SiMe3)3)X(THF)]2 between 210 and 250 °C afforded zinc metal in 97–99% yield, Si(SiMe3)3X in 91–94% yield, and THF in 81–98% yield. Density functional theory calculations confirmed that zinc formation becomes energetically favorable upon THF loss. Similar reactions are likely to be general for M(SiR3)n/MXn pairs and may lead to new metal-film-growth processes for chemical vapor deposition and atomic layer deposition.

THERMODYNMICS AND STRUCTURE OF POLY(ETHYLENE OXIDE) IN MIXTURES OF WATER AND ETHANOL

Poly(ethylene oxide) (PEO) is one of the most researched synthetic polymers due to the complex behavior which arises from the interplay of the hydrophilic and hydrophobic sites on the polymer chain. PEO in ethanol forms an opaque gel-like mixture with a partially crystalline structure. Addition of a small amount of water disrupts the gel: 5 wt % PEO in ethanol becomes a transparent solution with the addition of 4 vol % water. The phase behavior of PEO in mixed solvents have been studied using small-angle neutron scattering (SANS). PEO solutions (5 wt % PEO) which contain 4 vol % - 10 vol % (and higher) water behave as an athermal polymer solution and the phase behavior changes from UCST to LCST rapidly as the fraction of water is increased. 2 wt % PEO in water and 10 wt % PEO in ethanol/ water mixtures are examined to assess the role of hydration. The observed phase behavior is consistent with a hydration layer forming upon the addition of water as the system shifts from UCST to LCST behavior. At the molecular level, two or three water molecules can hydrate one PEO monomer (water molecules form a sheath around the PEO macromolecule) which is consistent with the suppression of crystallization and change in the mentioned phase behavior as observed by SANS. The clustering effect of aqueous PEO solution (M.W of PEO = 90,000 g/mol) is monitored as an excess scattering intensity at low-Q. Clustering intensity at Q = 0.004 Å^-1 is used for evaluating the clustering effect. The clustering intensity is proportional to the inverse temperature and levels off when the temperature is less than 50 ˚C. When the temperature is increased over 50 ˚C, the clustering intensity starts decreasing. The clustering of PEO is monitored in ethanol/ water mixtures. The clustering intensity increases as the fraction of water is increased. Based on the solvation intensity behavior, we confirmed that the ethanol/ water mixtures obey a random solvent mixing rule, whereby solvent mixtures are better at solvating the polymer that any of the two solvents. The solution behavior of PEO in ethanol was investigated in the presence of salt (CaCl2) using SANS. Binding of Ca2+ ions to the PEO oxygens transforms the neutral polymer to a weakly charged polyelectrolyte. We observed that the PEO/ethanol solution is better solvated at higher salt concentration due to the electrostatic repulsion of weakly charged monomers. The association of the Ca2+ ions with the PEO oxygen atoms transforms the neutral polymer to a weakly charged polyelectrolyte and gives rise to repulsive interactions between the PEO/Ca2+ complexes. Addition of salt disrupts the gel, which is consistent with better solvation as the salt concentration is increased. Moreover, SANS shows that the phase behavior of PEO/ethanol changes from UCST to LCST as the salt concentration is increased.

Immobilisation of heavy metal in cement-based solidification/stabilisation: a review

Heavy metal-bearing waste usually needs solidification/stabilization (s/s) prior to landfill to lower the leaching rate. Cement is the most adaptable binder currently available for the immobilisation of heavy metals. The selection of cements and operating parameters depends upon an understanding of chemistry of the system. This paper discusses interactions of heavy metals and cement phases in the solidification/stabilisation process. It provides a clarification of heavy metal effects on cement hydration. According to the decomposition rate of minerals, heavy metals accelerate the hydration of tricalcium silicate (C3S) and Portland cement, although they retard the precipitation of portlandite due to the reduction of pH resulted from hydrolyses of heavy metal ions. The chemical mechanism relevant to the accelerating effect of heavy metals is considered to be H+ attacks on cement phases and the precipitation of calcium heavy metal double hydroxides, which consumes calcium ions and then promotes the decomposition Of C3S. In this work, molecular models of calcium silicate hydrate gel are presented based on the examination of Si-29 solid-state magic angle spinning/nuclear magnetic resonance (MAS/NMR). This paper also reviews immobilisation mechanisms of heavy metals in hydrated cement matrices, focusing on the sorption, precipitation and chemical incorporation of cement hydration products. It is concluded that further research oil the phase development during cement hydration in the presence of heavy metals and thermodynamic modelling is needed to improve effectiveness of cement-based s/s and extend this waste management technique. (C) 2008 Elsevier Ltd. All rights reserved.

Aspects of the in vitro bioactivity of hydraulic calcium (alumino)silicate cement

In response to a burgeoning interest in the prospective clinical applications of hydraulic calcium (alumino)silicate cements, the in vitro bioactivity and dissolution characteristics of a white Portland cement have been investigated. The formation of an apatite layer within 6 h of contact with simulated body fluid was attributed to the rapid dissolution of calcium hydroxide from the cement matrix and to the abundance of pre-existing Si-OH nucleation sites presented by the calcium silicate hydrate phase. A simple kinetic model has been used to describe the rate of apatite formation and an apparent pseudo-second-order rate constant for the removal of HPO42- ions frorn solultion has been calculated (k(2) = 5.8 x 10(-4) g mg(-1)). Aspects of the chemistry of hydraulic cements are also discussed with respect to their potential use in the remedial treatment of living tissue. (C) 2008 Wiley Periodicals, Inc. J Biomed Mater Res 90A: 166-174, 2009

Characterization of carbonated tricalcium silicate and its sorption capacity for heavy metals: A micron-scale composite adsorbent of active silicate gel and calcite

Adsorption-based processes are widely used in the treatment of dilute metal-bearing wastewaters. The development of versatile, low-cost adsorbents is the subject of continuing interest. This paper examines the preparation, characterization and performance of a micro-scale composite adsorbent composed of silica gel (15.9 w/w%), calcium silicate hydrate gel (8.2 w/w%) and calcite (75.9 w/w%), produced by the accelerated carbonation of tricalcium silicate (C(3)S, Ca(3)SiO(5)). The Ca/Si ratio of calcium silicate hydrate gel (C-S-H) was determined at 0.12 (DTA/TG), 0.17 ((29)Si solid-state MAS/NMR) and 0.18 (SEM/EDS). The metals-retention capacity for selected Cu(II), Pb(II), Zn(II) and Cr(III) was determined by batch and column sorption experiments utilizing nitrate solutions. The effects of metal ion concentration, pH and contact time on binding ability was investigated by kinetic and equilibrium adsorption isotherm studies. The adsorption capacity for Pb(II), Cr(III), Zn(II) and Cu(II) was found to be 94.4 mg/g, 83.0 mg/g, 52.1 mg/g and 31.4 mg/g, respectively. It is concluded that the composite adsorbent has considerable potential for the treatment of industrial wastewater containing heavy metals.

X-ray crystallographic structures of two lamotrigine analogues: (I) 3,5-diamino-6-(2-chlorophenyl)-1,2,4-triazine water solvate and (II) 3,5-diamino-6-(3,6-dichlorophenyl)-1,2,4-triazine methanol solvate

The X-ray crystal structures of two lamotrigine derivatives (I) 3,5-diamino-6-(2-chlorophenyl)-1,2,4-triazine, C9H8ClN5, (465BL) as a hydrate, and (II) 3,5-diamino-6-(3,6-dichlorophenyl)-1,2,4-triazine, C9H7Cl2N5, (469BR) as a methanol solvate, have been carried out at liquid nitrogen temperature and room temperature, respectively. A detailed comparison of the two structures is given. Both are centrosymmetric with (I) in the orthorhombic space group Pbca, a = 12.2507(3), b = 15.7160(6), c = 21.71496(9) angstrom, Z = 16, and (II) in the monoclinic space group C2/c, a = 38.553(3), b = 4.9586(2), c = 14.546(2) angstrom, beta = 111.59(1)degrees, Z = 8. Final R indices [I > 2sigma(I)] for (I) are R1 = 0.0670, wR2 = 0.1515 and for (II) R1 = 0.0434, wR2 = 0.1185. Structure (I) has water of crystallization in the lattice and (II) includes a solvated CH3OH. Structure (I) is characterized by having two crystallographically independent molecules, A and B, of 465BL, per asymmetric unit. Molecule B has a very unusual feature in that the 2-chlorophenyl ring is statistically disordered, occupying site (1) in 87.5% of the structure and site (2) in 12.5% of the structure. Sites (1) and (2) are related by an exact 180 degrees pivot of the phenyl ring about the ring linkage bond. The presence of two independent molecules per asymmetric unit provides an ideal opportunity for the conformational flexibility of the molecule 465BL to be studied. Structure (I) also includes a further unusual feature in that the lattice contains one fully occupied water molecule and an additional solvated water which is only 33% occupied.

Co-melt fluidised bed granulation of pharmaceutical powders: Improvements in drug bioavailability

This study investigates the use of co-melt fluidised bed granulation for the agglomeration of model pharmaceutical powders, namely, lactose mono-hydrate, PEG 10000, poly-vinyl pyrolidone and ibuprofen as a model drug. Granulation within the co-melt system was found to follow a nucleationâ??steady growthâ??coating regime profile. Using high molecular weight PEG binder, the granulation mechanism and thus the extent of granulation was found to be significantly influenced by binder viscosity. The compression properties of the granulate within the hot fluidised bed were correlated using a novel high temperature experimental procedure. It was found that the fracture stress and fractural modulus of the materials under hot processing conditions were orders of magnitude lower than those measured under ambient conditions. A range of particle velocities within the granulator were considered based on theoretical models. After an initial period of nucleation, the Stokes deformation number analysis indicated that only velocities within the high shear region of the fluidised bed were sufficient to promote significant granule deformation and therefore, coalescence. The data also indicated that larger granules de-fluidised preventing agglomeration by coalescence. Furthermore, experimental data indicated that dissipation of the viscous molten binder to the surface was the most important factor in the latter stages of the granulation process. From a pharmaceutical perspective the inclusion of the model drug, ibuprofen, combined with PVP in the co-melt process proved to be highly significant. It was found that using DSC analysis on the formulations that the decrease in the heat of fusion associated with the melting of ibuprofen within the FHMG systems may be attributed to interaction between PVP and ibuprofen through inter-molecular hydrogen bonding. This interaction decreases the crystallinity of ibuprofen and facilitates solubilisation and bioavailability within the solid matrix.

Chemoenzymatic synthesis of enantiopure dihydroxy-1,2,3,4-tetrahydronaphthalenes from naphthalene and dihydronaphthalene precursors

cis-Dihydrodiol, cis-tetrahydrodiol and arene hydrate bacterial metabolites, of naphthalene and 1,2-dihydronaphthalene, have been used as synthetic precursors; chemoenzymatic and enzyme-catalysed syntheses have been used to obtain all possible enantiopure samples of dihydroxy-1,2,3,4-tetrahydronaphthalene stereoisomers.

Utilization of analgesics, sedatives, and pain scores in infants with a prolonged hospitlaization: A prospective descriptive cohort study

Aim
Describe the utilization of analgesic and sedative medications and documentation of pain scores in a cohort of critically ill infants in a neonatal intensive care unit.

Method
A prospective, longitudinal, cohort study of infants with a predicted length of stay =28 days. Dosages and routes of administration of analgesic and sedative medications and documentation of pain scores were collected on a daily basis.

Results
55 infants were enrolled into the study. Oral sucrose was administered to all 55 infants, 51 infants (93%) were administered enteral acetaminophen and 50 (91%) infants were administered morphine during their hospitalization. Sedatives were administered to 42 infants (76%); 36 (65%) were administered chloral hydrate and 32 (58%) were administered intravenous midazolam. With the exception of the first week of admission, when there was highest utilization of opioids and lower use of sucrose, acetaminophen and sedatives, the pattern of administration of analgesic and sedative agents remained relatively constant throughout the hospitalization. Pain scores were documented for 36 (65%) infants during their hospitalisation, however for these 36 infants, pain scores were infrequently recorded.

Conclusion
There was substantial and varied analgesic and sedative use in this cohort of infants, yet infrequent documentation of pain assessment scores. These practices highlight important clinical implications for sick infants requiring careful consideration of pain and distress management.

Synthesis of a tetraoxy-bis-nortaxadiene, en route to taxol, using a cascade radical cyclisation sequence

Concise syntheses of the substituted enynediones 28a, 33b and 36 starting from the cyclohexenealdehyde 18, corresponding to ring A in the taxanes, and the vinylstannane 24, are described. Treatment of 36 with Bu3SnH–AIBN did not lead to the oxy-substituted taxadiene 37 expected from a tandem radical macrocyclisation–radical transannulation sequence; instead, a mixture of unidentified products resulted. When the PMB ether 33b corresponding to the alcohol 36 was treated with Bu3SnH–AIBN under similar conditions, p-anisaldehyde was isolated, as a major by-product, but no evidence for the formation of a taxadiene could be observed. In contrast, the iododienynedione 41, i.e., deoxy 36, underwent a tandem radical macrocyclisation–transannulation sequence, when treated with Bu3SnH–AIBN, leading to the tetraoxy-bis-nortaxadiene 42 in 44% yield. Attempts to synthesise the alcohol 28b from the silyl ether 28a en route to the iodide 28c instead gave the substituted tetrahydrofuran 29 via an intramolecular oxy-Michael reaction.