An approach to 2,4,5-trisubstituted piperidines is reported, in which the key step is the Prins or carbonyl ene cyclisation of aldehydes of the type 1. Prins cyclisation catalysed by concentrated hydrochloric acid in CH(2)Cl(2) at -78 degrees C afforded good yields of two of the four possible diastereomeric piperidines, with the 4,5-cis product 7 predominating in a diastereomeric ratio of up to...

Treatment of 5-(tert-butyldimethylsilyl)-2,3-O-isopropylidene-D-ribose with lithium acetylides gave mixtures of syn- and anti-alkynols 2a-2c which were separated following protection as methoxymethyl ethers. These were converted to the corresponding iodides which underwent 6-exo-dig radical cyclisation to afford chiral cyclohexanes and carbasugars. Oxidation of the primary alcohols 6a-b gave th...

The first examples of 3,3-diaryloxetanes are prepared in a lithium-catalyzed and substrate dependent divergent Friedel-Crafts reaction. para-Selective Friedel-Crafts reactions of phenols using oxetan-3-ols afford 3,3-diaryloxetanes by displacement of the hydroxy group. These constitute new isosteres for benzophenones and diarylmethanes. Conversely, ortho-selective Friedel-Crafts reactions of ph...

An efficient diastereo- and enantioselective Friedel-Crafts alkylation of indoles with 3-nitro-2H-chromenes catalyzed by diphenylamine-linked bis(oxazoline) and bis(thiazoline) Zn(II) complexes has been developed. This asymmetric Friedel-Crafts alkylation led to medicinally privileged indolyl(nitro)chromans in good yields with high enantioselectivities (up to 95% ee) and diastereoselectivities ...

An interesting rearrangement of arylvinylidenecyclopropanes having three substituents at the 1- and 2-positions of the corresponding cyclopropane catalyzed by Lewis acids to give 6aH-benzo[c]fluorine derivatives via a double intramolecular Friedel-Crafts reaction or to give an indene derivative via an intramolecular Friedel-Crafts reaction is described.

Cyclopropabenzaindoles (CBIs) are exquisitely potent cytotoxins which bind and alkylate in the minor groove of DNA. They are not selective for cancer cells, so prodrugs are required. CBIs can be formed at physiological pH by Winstein cyclisation of 1-chloromethyl-3-substituted-5-hydroxy-2,3-dihydrobenzo[e]indoles (5-OH-seco-CBIs). Corresponding 5-NH2-seco-CBIs should also undergo Winstein cycli...

The synthesis of a range of fluorinated heterocycles is described via a Lewis acid-mediated Prins-type cyclisation.

A new concise route to Polycyclic Aromatic Hydrocarbons (PAHs) through radical addition and cyclisation of xanthates is described.

Computationally-enriched crafts are activities that blend the advantages of computational media with the affective, social, and cognitive affordances of children's crafts. In this paper, we describe a design application, Popup Workshop, whose purpose is to introduce children to the craft (and engineering discipline) of pop-up design in paper. We describe the fundamental ideas behind computation...

The first reported intramolecular pinacol coupling of cyclopropyl ketones has been achieved, demonstrating that cyclisation competes favourably with ring-opening of the cyclopropyl ketyl radical.