METAL CATALYZED CARBON-CARBON BOND FORMING REACTIONS

The total synthesis of medicinally active compounds are important pursuits
in the field of biomedical science. In line with our interest in the
efficient total synthesis of biological active natural products, we are
pursuing a program of research directed toward new carbon-carbon bond
construction reactions, which simplify the assembly of the carbon back bone
in complex natural products. The proposed research specifically examines the intramolecular iron(O)
catalyzed diene to olefin cross-coupling reaction which have been
underutilized as methodology for the preparation of functionalized carbo-
and hetercyclic ring systems. The chemistry proceeds with novel aspects of
regio- and stereochemical control including potential applications to
transition metal catalyzed asymmetric synthesis. Detailed chemical studies
of each of these aspects are proposed. The specific goals of our investigations in this research area are to
define catalyst and substrate requirements which enable; 1) the efficient
cross-coupling reaction at or near ambient temperatures; 2) the selection
of, on the basis of metal center steric and stereoelectronic requirements,
regioselective coupling to unsymmetrically substituted 1,3-dienes; 3) the
use of the metal center as a template to control the relative
stereochemistry in the bond formation between the two coordinated
substrates; 4) the high levels of asymmetric induction by coordinating
chiral ligands to the metal center; and 5) isolate and characterize new
organometallic complexes relevant to the completion of the above objectives. By virtue of the highly versatile functionality which is retained on either
side of the newly formed carbon-carbon bond, we anticipate that this
chemistry will be broadly applicable to the improved syntheses of
medicinally important compounds.