Catalytic asymmetric synthesis of a potent thiomarinol antibiotic.
Thiomarinols, isolated from the bacterium Alteromonas rava sp. nov. SANK 73390, are potent marine antibiotics that possess both Gram-positive and Gram-negative activity. The first total synthesis of a member of the thiomarinol class of marine antibiotics was achieved in a remarkable global yield of 22% (from 3-boronoacrolein pinacolate). The highlight of this synthesis is the efficient catalytic enantio-, regio-, E/Z-, and diastereoselective three-component inverse electron demand Diels-Alder/allylboration sequence. This key operation provides a rare example of an enantioselective HDA reaction involving acyclic 2-substituted enol ethers, and it featured an unusual but fortuitous kinetic selection that favored the requisite Z-dienophile.
Gao
Xuri
X
Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2, Canada.
Hall
Dennis G
DG
D020591:Alteromonas / Q000737:chemistry; D000900:Anti-Bacterial Agents / Q000138:chemical synthesis*; D002384:Catalysis; D016712:Mupirocin / Q000031:analogs & derivatives / Q000138:chemical synthesis*; D011714:Pyrans / Q000138:chemical synthesis; D013237:Stereoisomerism
D000900:Anti-Bacterial Agents; D011714:Pyrans; C085617:thiomarinol; D016712:Mupirocin