Total synthesis of formamicin.
The enantioselective total synthesis of the cytotoxic plecomacrolide natural product formamicin (1) is described. Key aspects of this synthesis include the efficient transacetalation reactions of MOM ethers 28 and 38 to form the seven-membered formyl acetals 29 and 39, a late-stage Suzuki cross-coupling reaction of the highly functionalized vinyl boronic acid 6 and vinyl iodide 7, a highly beta-selective glycosidation reaction of beta-hydroxy ketone 4 with 2,6-dideoxy-2-iodoglucopyranosyl fluoride 3, and the global desilylation of penultimate intermediate 77 mediated by in situ generated Et(3)N.2HF.
Department of Chemistry, University of Michigan, 930 North University, Ann Arbor, Michigan 48109, USA.
Timothy B
TB
Durham
Nicolas
N
Blanchard
Brad M
BM
Savall
Noel A
NA
Powell
William R
WR
Roush
D006031:Glycosylation; D018942:Macrolides / Q000138:chemical synthesis*; D013237:Stereoisomerism
D018942:Macrolides; C111293:formamicin