Total synthesis of (-)- and (+)-membrenone C.
[reaction: see text] A synthesis of the polypropionate marine defense substance (+)-membrenone C and its enantiomer that starts from (S)-2-methyl-3-(tert-butyldimethylsilyloxy)propanal is described. Key steps include (1) additions of chiral allenylmetal reagents to effect both chain homologation and the concomitant introduction of four stereo centers, (2) a bis-intramolecular hydrosilylation-oxidation sequence to install beta-hydroxy ketone subunits, and (3) a bis-intramolecular aldol reaction to construct the two dihydropyrone termini.
Marshall
James A
JA
Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904, USA. jam5x@virginia.edu
Ellis
Keith C
KC
D003500:Cyclization; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D010084:Oxidation-Reduction; D011753:Pyrones / Q000138:chemical synthesis*; D012833:Siloxanes; D013237:Stereoisomerism
D007202:Indicators and Reagents; D011753:Pyrones; D012833:Siloxanes; C430547:membrenone C