Chirality Transfer in Electrophilic Reactions of Hydrovinylation Adducts
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Date
2008-06
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Publisher
The Ohio State University
Abstract
As a result of new regulatory requirements and a deeper understanding of the role of chirality
in biological systems, the modern pharmaceutical industry has become dependent on chemical processes
which can selectively produce enantiopure compounds without wasteful resolutions. The
asymmetric hydrovinylation reaction has been demonstrated to yield a number of popular NSAIDs
with exceptionally high selectivity. The major thrust of this project was to examine how well chirality
could be transferred from an asymmetric center installed by the hydrovinylation to a new chiral
center formed with an achiral electrophilic reagent. The highest levels of selectivity were observed
for dihydroxylation and oxymercuration reactions, both of which employed sterically demanding
third row transition metal reagents. In addition to investigating selectivity, the photochemical
Barton reaction was examined as a route to functionalize methyl groups that result from the hydrovinlation
of terminal ole ns. Preliminary scouting experiments suggest the Barton reaction may
provide a viable route to functionalization.
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Keywords
diastereoselectivity, photochemistry, hydrovinylation