%0 Generic
%9 Doctoral Dissertation
%A Painter, Thomas Oliver
%D 2009
%F pittir:6482
%K allene-yne; carbocyclization; cycloaddition; cyclocarbonylation; cycloisomerization; lactams; transition metal
%T Cycloisomerization and Carbocyclization Reactions of Allenes for the Synthesis of Cross-Conjugated Trienes and Tryptophan-Derived Scaffolds
%U http://d-scholarship-dev.library.pitt.edu/6482/
%X A strategy for the preparation of 3-vinyl-2-alkylidene-3-cyclohexen-1-ones has been developed using an intramolecular rhodium(I)-catalyzed carbocyclization reaction of allene-ynones. Application of this strategy towards the preparation of analogs of the anticancer agent irofulven was realized, leading to highly functionalized spiro[2.5]octatrienes.A novel approach to ε-lactams from allene-containing propargyl amides has been achieved, also using the rhodium(I)-catalyzed carbocyclization reaction. Further elaboration of this strategy has afforded triene-containing azepines and a pyrroloazepinone.A diverging diversity-oriented synthesis (DOS) strategy using tryptophan as a key starting material was investigated. Constructon of allenic tetrahydro-β-carboline scaffolds via a Pictet-Spengler reaction and subsequent silver(I)-catalyzed cycloisomerization afforded tetrahydroindolizinoindoles. Conversion of the tetrahydro-β-carboline to an allenic propiolamide followed by a microwave-assisted allenic [2 + 2] cycloaddition reaction provided tetrahydrocyclobutaindoloquinolizinones. An allene-yne substituted derivative of tryptophan gave indolylmethylazabicyclooctadiene when subjected to a microwave-assisted allenic [2 + 2] cycloaddition reaction. This same tryptophan-derived precursor afforded an indolylmethyldihydrocyclopentapyridinone when subjected to a rhodium(I)-catalyzed cyclocarbonylation reaction.