Can acyclic conformational control be achieved via a sulfur-fluorine gauche effect?

The gauche conformation of the 1,2-difluoroethane motif is known to involve stabilising hyperconjugative interactions between donor (bonding, σC-H) and acceptor (antibonding, σ*C-F) orbitals. This model rationalises the generic conformational preference of F-Cβ-Cα-X systems (φFCCX ≈ 60°), where X is an electron deficient substituent containing a Period 2 atom. Little is known about the corresponding Period 3 systems, such as sulfur and phosphorus, where multiple oxidation states are possible. Conformational analyses of β-fluorosulfides, -sulfoxides and -sulfones are disclosed here, thus extending the scope of the fluorine gauche effect to the 3rd Period (F-C-C-S(O) n ; φFCCS ≈ 60°). Synergy between experiment and computation has revealed that the gauche effect is only pronounced in structures bearing an electropositive vicinal sulfur atom (S+-O-, SO2)

High Resolution Spectroscopy and Spectropolarimetry of some late F-/early G-type sun-like stars as targets for Zeeman Doppler imaging

High resolution spectroscopy and spectropolarimetry have been undertaken at the Anglo-Australian Telescope in order to identify suitable targets for magnetic studies of young sun-like stars, for the proxy study of early solar evolution. This study involved the investigation of some variable late F-/early G-type sun-like stars originally identified by the Hipparcos mission. Of the 38 stars observed for this study, HIP 31021, HIP 64732, HIP 73780 were found to be spectroscopic binary stars while HIP 19072, HIP 67651 and HIP 75636 are also likely to be binaries while HIP 33111 could even be a triple system. Magnetic fields were detected on a number of the survey stars: HIP 21632, HIP 43720, HIP 48770, HIP 62517, HIP 71933, HIP 77144, HIP 89829, HIP 90899 and HIP 105388, making these stars good candidates for follow-up Zeeman Doppler imaging studies.Comment: 16 pages, 16 figures, 4 tables Accepted for publication in PAS

Target selection for the SUNS and DEBRIS surveys for debris discs in the solar neighbourhood

Debris discs - analogous to the Asteroid and Kuiper-Edgeworth belts in the Solar system - have so far mostly been identified and studied in thermal emission shortward of 100 um. The Herschel space observatory and the SCUBA-2 camera on the James Clerk Maxwell Telescope will allow efficient photometric surveying at 70 to 850 um, which allow for the detection of cooler discs not yet discovered, and the measurement of disc masses and temperatures when combined with shorter wavelength photometry. The SCUBA-2 Unbiased Nearby Stars (SUNS) survey and the DEBRIS Herschel Open Time Key Project are complimentary legacy surveys observing samples of ~500 nearby stellar systems. To maximise the legacy value of these surveys, great care has gone into the target selection process. This paper describes the target selection process and presents the target lists of these two surveys.Comment: 67 pages with full tables, 7 figures, accepted to MNRA

Transits across a Cyclopentadienyl: Organic and Organometallic Haptotropic Shifts

references cited therein. (13) Electron acceptors which are also conjugated with the alkene r system will polarize the HOMO in the same directions as, but to a smaller extent than, Inductive acceptors.8 (14) There has been a suggestion that Me is an acceptor relative to H when attached to an sp3 carbon [C. A. Grob, Angew. Chem. lnt. Ed. Engl., 15, 569 (1976), and references cited therein]. The product ratio discussed here reflect this, but the IP changes do not. A subtle role of solvent may be involved. (15) J. Bastideand J. P. Maier, Chem. Phys., 12, 144 (1976 Li+, CUR+), the e component of which greatly stabilizes the most symmetrical q5 coordination. The lower the energy of the e acceptor set and the better the overlap with its Cp counterpart, the more are q2 and q5 stabilized relative to 7'. In the case of XH3+ (X = C, Si, Ge, Sn) an e acceptor orbital moves to lower energy as one proceeds down the group, and this is responsible for the decreasing barrier for sigmatropic shifts in CpXH3. The XH2 case, which yields a number of interesting collapse structures, is analyzed in detail for X, a main group center. Contrast the interaction of a cyclopentadienide anion and a proton with the interaction of the same anion and a Mn(CO)3+ fragment. Both result in stable molecules: cyclopentadiene (1) and V~-C~M~( C O )~ (2). But what a difference in the equilibrium geometries of these end products of the interaction! If we focus our attention on the cyclopentadienide site where the interacting partner settles down, then the proton chooses a position near to one carbon of the ring, but the Mn(C0)3+ fragment sits directly over the center of the ring. The ramifications of this differential are the concern of this paper. We will examine the interaction of a cyclopentadienide (CsHs-, Cp) ion with an interacting group X, X = H+, CH3+, SiR3+, Mn(C0)3+, CH22f, CH2. The result will consist of some conclusions concerning the equilibrium geometry of CpX as well as the relative energetics of the various haptotropic reactions of this Consider the passage of the interacting group X across the face of a Cp molecule, moving as indicated in 3 in a plane parallel to the Cp ring. Let the distance d be a separation at which there is sizable interaction between the frontier orbitals of X and the Cp a system. For a surface so constrained the asymmetric unit that need be calculated consists of the shaded area in 4, and two of the three boundaries of that area are contained in a transit along a line shown in projection in 5. Mirror symmetry is maintained at all points. The numbers nq shown along that line are convenient labels invoking a connection to the inorganic 7" notation* for denoting an approximate coordination geometry. In order to avoid confusion with structure numbers and ring carbon numbers, we have labeled the various sites along the transit line as 17, 217, . . . , 57. The site labeled 17, or some geometry near it, corresponds to or simple u interaction, such as we have in the collapse product cyclopentadiene. The 7IS site 57 is where one better come up with maximum stabilization for X = Mn(C0)3+. The site labeled 27 positions X over the center of a bond, and obviously will describe the important transition state region for a sigmatropic shift of a system like cyclopentadiene. 37 and 47 are not so easily defined. Experimentally, slippage of Cp rings from q5 coordination is often observed and q3 or q4 coordination may or may not be invoked. Somewhat arbitrarily we define 317 at the intersection of the transit line with the line joining C-2 and C-5 projected on the transit plane. The tetrahapto coordination site is most ambiguous (it could be near 37 or near 57), and SO we will not label any position as such. The analysis will consist of an inspection of interaction diagrams for the orbitals of Cp and X, as the ligand X and its position along the transit are varied. The qualitative arguments based on symmetry and overlap are supported by extended Huckel calculations whose details are given in the Appendix. The reader should be aware that this is an approximate metho

A Versatile cascade of intramolecular vilsmeier-haack and azomethine ylide 1,3-dipolar cycloaddition toward tricyclic cores of alkaloids

Abstract: In the pursuit of synthetic efficiency, we developed an innovative one-pot transformation of linear substrates into bi- and tricyclic adducts using a cascade of amide activation, nucleophilic cyclization, azomethine ylide generation, and subsequent inter- or intramolecular 1,3-dipolar cycloaddition. Despite the high density and variety of functional groups on the substrates, the sequence occurred with perfect chemoselectivity with good to excellent yields

Neurology

Contains reports on eight research projects.United States Air Force (AF33(616)-7588, AF49(638)-1130)National Science Foundation (Grant G-16526)United States Army Chemical Corps (DA-18-108-405-Cml-942)United States Public Health Service (B-3055, B-3090)United States Navy, Office of Naval Research (Contract Nonr-1841(70)

X-231A demonstration of in-situ remediation of DNAPL compounds in low permeability media by soil fracturing with thermally enhanced mass recovery or reactive barrier destruction

The overall goal of the program of activities is to demonstrate robust and cost-effective technologies for in situ remediation of DNAPL compounds in low permeability media (LPM), including adaptations and enhancements of conventional technologies to achieve improved performance for DNAPLs in LPM. The technologies sought should be potential for application at simple, small sites (e.g., gasoline underground storage tanks) as well as at complex, larger sites (e.g., DOE land treatment units). The technologies involved in the X-231A demonstration at Portsmouth Gaseous Diffusion Plant (PORTS) utilized subsurface manipulation of the LPM through soil fracturing with thermally enhanced mass recovery or horizontal barrier in place destruction. To enable field evaluation of these approaches, a set of four test cells was established at the X-231A land treatment unit at the DOE PORTS plant in August 1996 and a series of demonstration field activities occurred through December 1997. The principal objectives of the PORTS X-231A demonstration were to: determine and compare the operational features of hydraulic fractures as an enabling technology for steam and hot air enhanced soil vapor extraction and mass recovery, in situ interception and reductive destruction by zero valent iron, and in situ interception and oxidative destruction by potassium permanganate; determine the interaction of the delivered agents with the LPM matrix adjacent to the fracture and within the fractured zone and assess the beneficial modifications to the transport and/or reaction properties of the LPM deposit; and determine the remediation efficiency achieved by each of the technology strategies

Weak capture of protons by protons

The cross section for the proton weak capture reaction $^1H(p,e^+\nu_e)^2H$ is calculated with wave functions obtained from a number of modern, realistic high-precision interactions. To minimize the uncertainty in the axial two-body current operator, its matrix element has been adjusted to reproduce the measured Gamow-Teller matrix element of tritium $\beta$ decay in model calculations using trinucleon wave functions from these interactions. A thorough analysis of the ambiguities that this procedure introduces in evaluating the two-body current contribution to the pp capture is given. Its inherent model dependence is in fact found to be very weak. The overlap integral $\Lambda^2(E=0)$ for the pp capture is predicted to be in the range 7.05--7.06, including the axial two-body current contribution, for all interactions considered.Comment: 17 pages RevTeX (twocolumn), 5 postscript figure