Date of Award

Spring 2013

Document Type


First Advisor

Dr. C. Wade Downey

Second Advisor

Dr. Kristine A. Nolin


Through an efficient one-pot reaction sequence, ethyl propiolate can be transformed into a complex, usefully functionalized bicyclic product. Thioconjugate addition yielding Z-selective enoates has been developed for both aromatic thiols (trialkylamine-catalyzed) and aliphatic thiols (KOt-Bu-catalyzed). The oxidation of the thioenoates thus generated is followed by Li-catalyzed oxidation to sulfones using mCPBA, and Li-catalyzed Diels–Alder addition of cyclopentadiene. These subsequent steps are performed in situ, without any purification of intermediates. The yields obtained using the described synthesis are acceptable for a one-pot three-step sequence. Preliminary conjugate addition results with alcohols and amines as nucleophiles are also presented.

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