Carbon–Carbon Bond-Forming
Reactions
of α-Thioaryl Carbonyl Compounds for the Synthesis of Complex
Heterocyclic Molecules
- Publication date
- Publisher
Abstract
Strategies for the formation of carbon–carbon
bonds from
the α-thioaryl carbonyl products of substituted lactams are
described. Although direct functionalization is possible, a two step
process of oxidation and magnesium-sulfoxide exchange has proven optimal.
The oxidation step results in the formation of two diastereomers that
exhibit markedly different levels of stability toward elimination,
which is rationalized on the basis of quantum mechanical calculations
and X-ray crystallography. Treatment of the sulfoxide with <i>i</i>-PrMgCl results in the formation of a magnesium enolate
that will undergo an intramolecular Michael addition reaction to form
two new stereogenic centers. The relationship between the substitution
patterns of the sulfoxide substrate and the efficiency of the magnesium
exchange reaction are also described