Stereocontrolled synthesis of adjacent acyclic quaternary-tertiary motifs: application to a concise total synthesis of (-)-filiformin.
Lithiation/borylation methodology has been developed for the synthesis of acyclic quaternary-tertiary motifs with full control of relative and absolute stereochemistry, thus leading to all four possible isomers of a stereodiad. A novel intramolecular Zweifel-type olefination enabled acyclic stereocontrol to be transformed into cyclic stereocontrol. These key steps have been applied to the shortest enantioselective synthesis of (-)-filiformin to date (9 steps) with full stereocontrol.
School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS (UK).
Daniel J
DJ
Blair
Catherine J
CJ
Fletcher
Katherine M P
KM
Wheelhouse
Varinder K
VK
Aggarwal
D001897:Boronic Acids / Q000737:chemistry; D001969:Bromobenzenes / Q000138:chemical synthesis* / Q000737:chemistry; D002219:Carbamates / Q000737:chemistry; D004952:Esters; D008094:Lithium / Q000737:chemistry; D013237:Stereoisomerism
D001897:Boronic Acids; D001969:Bromobenzenes; D002219:Carbamates; D004952:Esters; C442621:filiformin; D008094:Lithium
boron; enantioselectivity; lithium; natural products; total synthesis