Asymmetric synthesis of quaternary centers. Total synthesis of (-)-malyngolide.
[structure] The deracemization of 3-nonyl-3,4-epoxybut-1-ene with Pd(0) in the presence of chiral ligands using p-methoxybenzyl alcohol as a nucleophile proceeds regio- and enantioselectively to form the monoprotected vinylglycidol in 99% ee. This chiral building block was converted in seven steps to (-)-malyngolide, an antibiotic showing significant activity against Mycobacterium smegmatis and Streptococcus pyogenes. An interesting aspect involves controlling the diastereoselectivity of protonation of an enolate via a distal hydroxyl group.
Trost
B M
BM
Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA. bmtrost@leland.stanford.edu
Tang
W
W
Schulte
J L
JL
D000478:Alkylation; D000900:Anti-Bacterial Agents / Q000138:chemical synthesis*; D000458:Cyanobacteria / Q000737:chemistry; D008024:Ligands; D011753:Pyrones / Q000138:chemical synthesis; D013237:Stereoisomerism
D000900:Anti-Bacterial Agents; D008024:Ligands; D011753:Pyrones; C065487:malyngolide