Weak refinement in Z

An important aspect in the specification of distributed systems is the role of the internal (or unobservable) operation. Such operations are not part of the user interface (i.e. the user cannot invoke them), however, they are essential to our understanding and correct modelling of the system. Various conventions have been employed to model internal operations when specifying distributed systems in Z. If internal operations are distinguished in the specification notation, then refinement needs to deal with internal operations in appropriate ways. However, in the presence of internal operations, standard Z refinement leads to undesirable implementations. In this paper we present a generalization of Z refinement, called weak refinement, which treats internal operations differently from observable operations when refining a system. We illustrate some of the properties of weak refinement through a specification of a telecommunications protocol

Atropselective syntheses of (-) and (+) rugulotrosin A utilizing point-to-axial chirality transfer

Chiral, dimeric natural products containing complex structures and interesting biological properties have inspired chemists and biologists for decades. A seven-step total synthesis of the axially chiral, dimeric tetrahydroxanthone natural product rugulotrosin A is described. The synthesis employs a one-pot Suzuki coupling/dimerization to generate the requisite 2,2'-biaryl linkage. Highly selective point-to-axial chirality transfer was achieved using palladium catalysis with achiral phosphine ligands. Single X-ray crystal diffraction data were obtained to confirm both the atropisomeric configuration and absolute stereochemistry of rugulotrosin A. Computational studies are described to rationalize the atropselectivity observed in the key dimerization step. Comparison of the crude fungal extract with synthetic rugulotrosin A and its atropisomer verified that nature generates a single atropisomer of the natural product.P50 GM067041 - NIGMS NIH HHS; R01 GM099920 - NIGMS NIH HHS; GM-067041 - NIGMS NIH HHS; GM-099920 - NIGMS NIH HH

BOEKBESPREKINGEN

BOEKBESPREKINGE

Synthesis of aminopyrazoles from sydnones and ynamides.

Aminopyrazoles are prepared from readily accessible sydnones and sulfonyl ynamides using either a copper-mediated sydnone alkyne cycloaddition (CuSAC) or in situ generated strained cyclic ynamides