Control of regioselectivity:oxidation and deprotection

Palladium is a highly versatile metal, capable of catalysing oxidations, reductions and a myriad of organic transformations. The inorganic chemistry of palladium, and the relation of this to the catalytic activity of the metal, is briefly discussed. A short survey of the range of palladiumcatalysed reactions is undertaken. The Wacker reaction, the palladium(II)-catalysed oxidation of alkenes to carbonyls, is considered in detail. In the absence of heteroatoms, the Wacker reaction of terminal alkenes is known to produce methyl ketones. However, it is shown that the Wacker reaction of styrenes is unusual; under reoxidant-free conditions, the reaction proceeds to give aldehydes as the major products. The scope of this transformation is probed with a series of ring-substituted styrenes: it is found to be general for all substituents studied. The mechanism responsible for this anti-Markovnikov regioselectivity is investigated. Palladium(0) is eliminated as a possible cause of unusual reactivity. NMR studies and reactions of suitable substrates are used to suggest a side-on complex of either an agostic or 4-type. Kinetic studies show no evidence of an agostic interaction, and thus an 4-complex is more likely. Attempts at achieving catalytic activity in the formation of aldehydes are unsuccessful with small-molecule reoxidants. However, the use of heteropolyacids is found to lead to a catalytic reaction. A second source of unexpected regioselectivity in the Wacker reaction is the agostic interaction of hydrogens on the allylic position with the palladium centre. Some new evidence is obtained for this effect in the reaction of 1-phenylbut-1-ene and 1-phenyl-3-methylbut-1-ene. Attempts are made to gain additional insight by seeking a kinetic isotope effect in the Wacker reaction of dec-1-ene and a partially-deuterated analogue. Some evidence of a kinetic isotope effect is found. The use of benzyl (Bn) groups is one of the most common methods used in synthesis to protect alcohols and amines. The method of choice for the removal of Bn groups is hydrogenolysis over a palladium catalyst. Oxidative deprotection methods are also available, particularly when the MPM (4-methoxybenzyl) group is used in place of Bn. The NAP (2-naphthylmethyl) protective group has recently been introduced and has been shown to be removed by hydrogenolysis more readily than Bn groups. The usefulness of the NAP group is extended: it is demonstrated that NAP is less sensitive to oxidative cleavage with CAN [hexa-amminecerium(IV) nitrate(V)] than MPM. A series of glucose-based substrates are prepared, and used to demonstrate this oxidative selectivity

Evidence for extended IR emission in NGC2798 and NGC6240

Extended emission at 10 and 20 microns can be used to distinguish starbursts from monsters as the underlying energy source driving the luminous infrared emission in the central regions of galaxies. The spatial extent of the mid infrared emission in the interacting galaxy NCG 2798 and the merger NGC 6240 were investigated. The 10 and 20 micron profiles of the IR source in NGC 2798 are significantly wider than beam profiles measured on a standard star, supporting a starburst interpretation of its IR luminosity. For NGC 6240 there is marginal evidence for an extended 10 micron source, suggesting that a significant fraction of its IR luminosity could be produced by a burst of star formation

Zinc calixarene complexes for the ring opening polymerization of cyclic esters

Reaction of Zn(C₆F₅)₂·toluene (two equivalents) with 1,3-dipropoxy-p-tert-butyl-calix[4]arene (L¹H₂) led to the isolation of the complex [{Zn(C₆F₅)}₂L¹] (1), whilst similar use of Zn(Me)₂ resulted in the known complex [{Zn(Me)}₂L¹] (2). Treatment of L¹H₂ with in situ prepared Zn{N(SiMe₃)₂}₂ in refluxing toluene led to the isolation of the compound [(Na)ZnN(SiMe₃)₂L¹] (3). The stepwise reaction of L¹H₂ and sodium hydride, followed by ZnCl₂ and finally NaN(SiMe₃)₂ yielded the compound [Zn{N(SiMe₃)₂}₂L¹] (4). The reaction between three equivalents of Zn(C₆F₅)₂·toluene and oxacalix[3]arene (L²H₃) at room temperature formed the compound {[Zn(C₆F₅)]₃L²} (5); heating of 5 in acetonitrile caused the ring opening of the parent oxacalix[3]arene and rearrangement to afford the complex [(L²)Zn₆(C₆F₅)(R)(RH)OH]·5MeCN R = C₆F₅CH₂-(p-ᵗBuPhenolate-CH₂OCH₂–)₂–p-ᵗBuPhenolate-CH₂O⁻)³⁻ (6). The molecular structures of the new complexes 1, 3 and 6, together with that of the known complex 2, whose solid state structure has not previously been reported, have been determined. Compounds 1, 3–5 have been screened for the ring opening polymerization (ROP) of ε-caprolactone (ε-CL) and rac-lactide. Compounds featuring a Zn–C₆F₅ fragment were found to be poor ROP pre-catalysts as they did not react with benzyl alcohol to form an alkoxide. By contrast, compound 4, which contains a zinc silylamide linkage, was the most active of the zinc-based calix[4]arene compounds screened and was capable of ROP at ambient temperature with 65% conversion over 4 h

Infrared images of merging galaxies

Infrared imaging of interacting galaxies is especially interesting because their optical appearance is often so chaotic due to extinction by dust and emission from star formation regions, that it is impossible to locate the nuclei or determine the true stellar distribution. However, at near-infrared wavelengths extinction is considerably reduced, and most of the flux from galaxies originates from red giant stars that comprise the dominant stellar component by mass. Thus near infrared images offer the opportunity to study directly components of galactic structure which are otherwise inaccessible. Such images may ultimately provide the framework in which to understand the activity taking place in many of the mergers with high Infrared Astronomy Satellite (IRAS) luminosities. Infrared images have been useful in identifying double structures in the nuclei of interacting galaxies which have not even been hinted at by optical observations. A striking example of this is given by the K images of Arp 220. Graham et al. (1990) have used high resolution imaging to show that it has a double nucleus coincident with the radio sources in the middle of the dust lane. The results suggest that caution should be applied in the identification of optical bright spots as multiple nuclei in the absence of other evidence. They also illustrate the advantages of using infrared imaging to study the underlying structure in merging galaxies. The authors have begun a program to take near infrared images of galaxies which are believed to be mergers of disk galaxies because they have tidal tails and filaments. In many of these the merger is thought to have induced exceptionally luminous infrared emission (cf. Joseph and Wright 1985, Sanders et al. 1988). Although the optical images of the galaxies show spectacular dust lanes and filaments, the K images all have a very smooth distribution of light with an apparently single nucleus

Adverse childhood experiences and deleterious outcomes in adulthood: A consideration of the simultaneous role of genetic and environmental influences in two independent samples from the United States

Background Adverse childhood experiences (ACEs) are a potent risk factor. Despite these findings, studies have also recognized the importance of considering additional sources of genetic and environmental influence that cluster within families. Objective To properly control for latent sources of genetic and within-family environmental influences and isolate the association between ACEs and the following outcomes in adulthood: physical health, depressive symptoms, educational attainment, income attainment, alcohol problems, and antisocial behavior. Participants and Setting Two independent samples of twins and siblings from the United States: the Midlife Development in the United States (MIDUS) study (N = 862) and the National Longitudinal Study of Adolescent to Adult Health (Add Health; N = 3112). Methods Sibling comparison models, which control for latent sources of genetic and within-family environmental influences, were estimated to examine whether differential exposure to ACEs was associated with the examined outcomes. Results Families that experienced more adversity also experienced more deleterious outcomes. However, siblings that experienced more adversity were no more likely to experience deleterious outcomes than their co-siblings. However, greater exposure to ACEs was associated with increases in depressive symptoms (Add Health). Additional models revealed that the similarity between siblings from the same family stemmed from latent sources of within-family environmental influences not captured by traditional ACEs measures. Conclusions Considering genetic influences and additional latent sources of within-family influences is crucial in isolating the effects of ACEs. Currently employed ACEs measures may not adequately capture the full range of impactful sources of family-level environmental influence

Evidence for a Molecular Cloud Origin for Gamma-Ray Bursts: Implications for the Nature of Star Formation in the Universe

It appears that the majority of rapidly-, well-localized gamma-ray bursts with undetected, or dark, optical afterglows, or `dark bursts' for short, occur in clouds of size R > 10L_{49}^{1/2} pc and mass M > 3x10^5L_{49} M_{sun}, where L is the isotropic-equivalent peak luminosity of the optical flash. We show that clouds of this size and mass cannot be modeled as a gas that is bound by pressure equilibrium with a warm or hot phase of the interstellar medium (i.e., a diffuse cloud): Such a cloud would be unstable to gravitational collapse, resulting in the collapse and fragmentation of the cloud until a burst of star formation re-establishes pressure equilibrium within the fragments, and the fragments are bound by self-gravity (i.e., a molecular cloud). Consequently, dark bursts probably occur in molecular clouds, in which case dark bursts are probably a byproduct of this burst of star formation if the molecular cloud formed recently, and/or the result of lingering or latter generation star formation if the molecular cloud formed some time ago. We then show that if bursts occur in Galactic-like molecular clouds, the column densities of which might be universal, the number of dark bursts can be comparable to the number of bursts with detected optical afterglows: This is what is observed, which suggests that the bursts with detected optical afterglows might also occur in molecular clouds. We confirm this by modeling and constraining the distribution of column densities, measured from absorption of the X-ray afterglow, of the bursts with detected optical afterglows: We find that this distribution is consistent with the expectation for bursts that occur in molecular clouds, and is not consistent with the expectation for bursts that occur in diffuse clouds. More...Comment: Accepted to The Astrophysical Journal, 22 pages, 6 figures, LaTe

Extragalactic infrared spectroscopy

The spectra of galaxies in the near infrared atmospheric transmission windows are explored. Emission lines were detected due to molecular hydrogen, atomic hydrogen recombination lines, a line attributed to FEII, and a broad CO absorption feature. Lines due to H2 and FEII are especially strong in interacting and merging galaxies, but they were also detected in Seyferts and normal spirals. These lines appear to be shock excited. Multi-aperture measurements show that they emanate from regions as large as 15 kpc. It is argued that starbursts provide the most plausible and consistent model for the excitation of these lines, but the changes of relative line intensity of various species with aperture suggest that other excitation mechanisms are also operating in the outer regions of these galaxies

Brachiopod Communities in Avonian Reef Limestones of the Pennines

Abstract Not Provided