Approaches to the stereoselective total synthesis of biologically active natural products

Abstract

Total syntheses of epothilone B and pamamycin 607, which feature reactions between functionalized allylstannanes and aldehydes to introduce a (Z)-trisubstituted double-bond and remote stereocenters stereoselectively, are discussed. Recent work concerned with carrying out this chemistry without the use of allylstannanes as starting materials and progress toward a total synthesis of bryostatins are also presented.

Concise Synthesis of the Bryostatin A-Ring via Consecutive C−C Bond Forming Transfer Hydrogenations

“…A formal synthesis of bryostatin 7 was reported by Hale . Finally, several creative synthetic approaches to bryostatin fragments are reported by Hale, Thomas, Hoffman, Vandewalle, Burke, and the present author . Although impressive, these syntheses do not represent a practical source of material for clinical study.…”

Enantioselective Reductive Coupling of Alkynes and α-Keto Aldehydes via Rhodium-Catalyzed Hydrogenation: An Approach to Bryostatin Substructures

“…This fact, coupled with the low natural abundance of the bryostatins, has stimulated efforts toward the preparation and evaluation of simplified analogous by Wender 7 and Keck . Finally, a number of creative synthetic approaches to various bryostatin fragments are reported by Hale, Thomas, Hoffman, Vandewalle, and Burke …”