Asymmetric Total Syntheses,Stereostructures, and Cytotoxicities of Marine Bromotriterpenoids Aplysiol B (Laurenmariannol) and Saiyacenol A

There are marine cytotoxic bromotriterpenoids, named the thyrsiferol family that are structurally characterized by some tetrahydropyran (THP) and tetrahydrofuran (THF) rings. The thyrsiferol family belongs to natural products that are often difficult to determine their stereostructures even by the current, highly advanced spectroscopic methods, especially in acyclic systems including stereogenic tetrasubstituted carbon centers. In such cases, it is effective to predict and synthesize the possible stereostructures. Herein, to elucidate ambiguous stereostructures and unassigned absolute configurations of aplysiol B, laurenmariannol, and saiyacenol A, members of the thyrsiferol family, we carried out their asymmetric chemical syntheses featuring 6-exo and 5-exo oxacyclizations of epoxy alcohol precursors and 6-endo bromoetherification of a bishomoallylic alcohol. In this paper, we report total assignments of their stereostructures through their asymmetric chemical syntheses and also their preliminary cytotoxic activities against some tumor cells. These results could not have been achieved without depending on asymmetric total synthesis.     

Localization effects and measure source terms in numerical schemes for balance laws

This paper investigates the behavior of numerical schemes for nonlinear conservation laws with source terms. We concentrate on two significant examples: relaxation approximations and genuinely nonhomogeneous scalar laws. The main tool in our analysis is the extensive use of weak limits and nonconservative products which allow us to describe accurately the operations achieved in practice when using Riemann-based numerical schemes. Some illustrative and relevant computational results are provided.

     

The first total syntheses of (±)-Preussomerins K and L using 2-arylacetal anion technology

The first syntheses of newly isolated members of the Preussomerin family, Preussomerins K and L, are reported. Key steps include the functionalisation of a 2-arylacetal anion, one-pot Friedel-Crafts cyclisation-deprotection and reductive opening of epoxides.     

Polynomial Quantization on Rank One Para-Hermitian Symmetric Spaces

We construct the polynomial quantization on the space G/H where G=SL(n,R),H=GL(n–1,R). It is a variant of quantization in the spirit of Berezin. In our case covariant and contravariant symbols are polynomials on G/H. We introduce a multiplication of covariant symbols, establish the correspondence principle, study transformations of symbols (the Berezin transform) and of operators. We write a full asymptotic decomposition of the Berezin transform.     

A Deformation-Theoretical Approach to Weyl Quantization on Riemannian Manifolds

By using a sheaf-theoretical language, we introduce a notion of deformation quantization allowing not only for formal deformation parameters but also for real or complex ones as well. As a model for this approach to deformation quantization, we construct a quantization scheme for cotangent bundles of Riemannian manifolds. Here, we essentially use a complete symbol calculus for pseudodifferential operators on a Riemannian manifold. Depending on a scaling parameter, our quantization scheme corresponds to normally ordered, Weyl or antinormally ordered quantization. Finally, it is shown that our quantization scheme induces a family of pairwise isomorphic strongly closed star products on a cotangent bundle.     

Remarks on a theorem of Taskinen on spaces of continuous functions

We clarify and prove in a simpler way a result of Taskinen about symmetric operators on C(Kⁿ), K an uncountable metrizable compact space. To do this we prove that, for any compact space K and any n ∈ ?, the symmetric injective n–tensor product of C(K), , is complemented in C(B_C(K)*), a result of independent interest. The techniques we develop allow us to extend the result in several directions. We also show that the hypothesis of metrizability and uncountability cannot be removed.     

Radical Couplings as Key Steps for the Preparation of Derivatives of Nonactic Acid

Summary. Free radical couplings from furan, as cheap starting material, were studied in view of developing a rapid strategy en route to the synthesis of derivatives of nonactin. The chain containing the alcohol function was introduced in one or two steps in 86% yield. For the introduction of the second chain with the ester function two different coupling methods were tested. Starting from the advanced intermediates obtained nonactin derivatives can be prepared by catalytic hydrogenation of the furan ring.