Directed metalation/ligand coupling approach to the enantioselective synthesis of 1,1′-binaphthyls

Introduction of a 2-isopropoxycarbonyl or 2-NN-dimethylcarbamoyl group into homochiral 1-p-tolyl- or 1-t-butyl-sulfinylnaphthalenes, via directed metalation reaction, followed by ligand coupling reaction with 1-naphthylmagnesium bromide, furnished atropisomeric 1,1′-binaphthyls in 82–95% enantiomeric excess (e.e.).     

Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (C_trs) determined using the Mayo method is equal to 3.8 × 10^?3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10^?3). Simulations, including chain‐length‐dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion–time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the M_n data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3620–3625, 2007     

Total synthesis of (±) maculalactone A, maculalactone B and maculalactone C and the determination of the absolute configuration of natural (+) maculalactone A by asymmetric synthesis

Maculalactones A, B and C from the marine cyanobacterium Kyrtuthrix maculans are amongst the only compounds based on the tribenzylbutyrolactone skeleton known in nature and (+) maculalactone A from the natural source possesses significant biological activity against various marine herbivores and marine settlers. We now report a concise synthesis of racemic maculalactone A in five steps from inexpensive starting materials. Maculalactones B and C were synthesized by a minor modification to this procedure, and the synthetic design also permitted an asymmetric synthesis of maculalactone A to be achieved in around 85% ee. The (+) and (−) enantiomers of maculalactone A were assigned, respectively, to the S and R configurations on the basis of the chiral selectivity expected for catecholborane reduction of an unsymmetrical ketone in the presence of Corey's oxazoborolidine catalyst. Surprisingly, it appeared that natural (+) maculalactone A was biosynthesized in K. maculans in a partially racemic form, comprising ca. 90-95% of the (S) enantiomer and 5-10% of its (R) enantiomer. Coincidentally therefore, the percentage enantiomeric excess of the product obtained from asymmetric synthesis almost exactly matched that found in nature.     

Echo planar imaging of perfluorocarbons

Emulsions of perfluorotributylamine (FTBA) and perflubron were evaluated for their utility in ¹⁹F echo planar imaging. Fluorine images of the emulsions were obtained in a phantom and two mice that had been predosed. Both agents, but particularly perflubron, show potential for fluorine echo planar studies because of the long spin-spin relaxation times of the CF₃ resonances. High resolution thin slice images obtained in as little as 26.6 ms are presented.     

Production of slow muonic hydrogen isotopes in vacuum

Muonic hydrogen isotopes (μ⁻ p, μ⁻ d, and μ⁻t) are simple quantum mechanical systems ideally suited for studies of numerous fundamental phenomena in electroweak and strong interactions as well as in applied areas such as muon chemistry or muon catalyzed fusion. Emission of muonic hydrogen isotopes into vacuum helps to overcome the limitations which are normally imposed on conventional investigations with gaseous and liquid targets. A proof of principle experiment for this new technique was performed at TRIUMF last year. Negative muons with 30 MeV/c momentum were stopped in a thin film of solid hydrogen and produced very low energy μ⁻d in vacuum. The distribution center of the normal velocity components of emitted μ⁻d atoms was measured to be ∼1 cm/μs. The yield of μ⁻d in vacuum is an increasing function of H₂ film thickness δ up to a value of δ≥1 mm.     

The biomarker concept — strengths and weaknesses

Summary This paper describes a simplified model which links the sedimentary concentration of selected biomarkers to their export primary production, their stability during transit to the anoxic sediment layer and the sediment bulk sedimentation rate. Manipulation of the biomarker data permits the individual effects of these processes to be separated. Examples demonstrate the use of this strategy in the evaluation of environmentally significant parameters.     

L-functions of second-order cusp forms

We discuss equivalent definitions of holomorphic second-order cusp forms and prove bounds on their Fourier coefficients. We also introduce their associated L-functions, prove functional equations for twisted versions of these L-functions and establish a criterion for a Dirichlet series to originate from a second order form. In the last section we investigate the effect of adding an assumption of periodicity to this criterion. 2000 Mathematics Subject Classification Primary—11F12, 11F66 G. Mason: Research supported in part by NSF Grant DMS 0245225. C. O’Sullivan: Research supported in part by PSC CUNY Research Award No. 65453-00 34.