Synthesis of chiral homoallylic alcohols and phthalans through the asymmetric allylation of carbonyl compounds /

The implementation of chiral centres within biologically active compounds has been a perplexing yet motivational force in chemistry. This work presents the attempted formation of a concurrent or sequential tandem catalyzed methodology of enantioselective nucleophilic addition and electrophilic cyclization. The 2'- arylalkynyl- aldehyde, ketone, and imine substrates used within were adeptly chosen with a dually activated structure; 1) for nucleophilic addition to the electrophilic substituents; and 2) for carbophilic activation of the alkyne substituent to undergo cyclization. To accomplish the nucleophilic addition, two distinct allylation methodologies were pursued: (/?)-BINOL catalyzed-allylboration and (5)- BINAP-AgF catalyzed-allylsilylation. BINAP catalyzed enantioselective allylation of 2'-arylalkynyl-aldehydes, to form chiral homoallylic alcohols, was successful. Homoallylic alcohols were isolated with high enantio-purity (>80%), which then underwent sequential cyclization to form chiral allylic phthalans, in moderate yields. An application of this methodology towards the construction of biologically active compounds was included with the partial synthesis of the natural product and H. pylori inhibitor, (+)-Spirolaxine methyl ether.

The neoliberalization of street vending policy in Lima, Peru: the politics of citizenship. property and public space in the production of a new urban marginality

Neoliberalism is having a significant and global impact on political, social and economic life across spaces. This work illustrates how neoliberalism is attempting to change the ways in which the urban poor - particularly those that participate in street vending - use urban spaces in Lima, Peru. Using municipal policies, newspaper articles and local academic texts I argue that there is a changing marginality in Lima that is being experienced by street vendors, and currently in los canas of Lima. In particular, I discuss formalization, a neoliberal strategy in street vending policy, which is used with eradication and social assistance strategies in attempts to re-regulate street vendors.