Mechanistic Studies on the Base-Promoted Ring Opening of Glycal-Derived -Dibromocyclopropanes.

In the presence of a nucleophilic base, ring-fused -dibromocyclopropanes derived from d-glycals undergo ring opening to give 2-deoxy-2-(-bromomethylene)glycosides. Such cleavage of an exocyclic cyclopropane bond contrasts with the more usual silver-promoted ring-expansion reactions in which endocyclic bond cleavage occurs. Experimental and theoretical studies are reported which provide insights into the reaction mechanism and the origin of its kinetic selectivity for -configured bromoalkene products.

The use and misuse of the Dix-Hallpike test in the emergency department.

Objectives: A simple bedside test, the Dix-Hallpike test (DHT), can reliably diagnose benign paroxysmal positional vertigo (BPPV) in patients with acute onset dizziness or vertigo. We evaluated patterns of DHT use by emergency physicians in patients presenting with dizziness and vertigo. Our objective was to assess the frequency and clinically appropriate use of the DHT in an emergency department.

Diagnostic Accuracy of the HINTS Exam in an Emergency Department: A Retrospective Chart Review.

Introduction: The HINTS exam is a series of bedside ocular motor tests designed to distinguish between central and peripheral causes of dizziness in patients with continuous dizziness, nystagmus, and gait unsteadiness. Previous studies, where the HINTS exam was performed by trained specialists, have shown excellent diagnostic accuracy. Our objective was to assess the diagnostic accuracy of the HINTS exam as performed by emergency physicians on patients presenting to the emergency department (ED) with a primary complaint of vertigo or dizziness.

Catalytic Asymmetric Staudinger-aza-Wittig Reaction for the Synthesis of Heterocyclic Amines.

Many natural products and medicinal drugs are heterocyclic amines possessing a chiral quaternary carbon atom in their heterocyclic ring. Herein, we report the first catalytic and asymmetric Staudinger-aza-Wittig reaction for the desymmetrization of ketones. This highly enantioselective transformation proceeds at room temperature to provide high yields-even on multigram scales-of nitrogen heterocycles featuring a chiral quaternary center.

Asymmetric synthesis of multiple quaternary stereocentre-containing cyclopentyls by oxazolidinone-promoted Nazarov cyclizations.

Carbometalation of oxazolidinone ()-substituted ynamides is used to generate highly substituted -divinyl (and aryl vinyl) ketones for use in Nazarov cyclizations. The -group serves as a remarkably effective chiral activating group, enabling the torquoselective Nazarov cyclization of these sterically congested substrates to be performed under mild conditions. It also serves as a charge-stabilizing group in the intermediate oxyallyl cation, suppressing undesired [1,2]-sigmatropic shifts of neighboring substituents and facilitating the regio- and stereoselective incorporation of nucleophiles to yield cyclopentanoids containing up to three contiguous all-carbon quaternary (4°) stereocentres.