Stereospecific Pd(0)-catalyzed arylation of an allylic hydroxy phosphonate derivative: formal synthesis of (S)-(+)-ar-turmerone.
Reaction of the (1S)-allylic hydroxy phosphonate 1(S) with methyl chloroformate in pyridine yields the corresponding carbonate 3(S). The carbonate 3(S) undergoes a palladium-catalyzed arylation with p-tolyl tributylstannane to give both the 1E and 1Z vinyl phosphonates 6 (85:15). The E and Z vinyl phosphonates 6 were shown to have the opposite configuration at C-3. The major vinyl phosphonate isomer (3S,1E), was converted to (3S)-3-(p-tolyl)-butanal 8(S), completing a formal total synthesis of (S)-ar-turmerone 5a.
Rowe
Bradley J
BJ
Department of Chemistry and Biochemistry, University of Missouri-St. Louis, 8001 Natural Bridge Road, St. Louis, Missouri 63121, USA.
Spilling
Christopher D
CD
D000498:Allyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D008956:Models, Chemical; D015394:Molecular Structure; D063065:Organophosphonates / Q000138:chemical synthesis* / Q000737:chemistry; D010165:Palladium / Q000737:chemistry*; D012717:Sesquiterpenes; D013237:Stereoisomerism; D013329:Structure-Activity Relationship; D014050:Toluene / Q000031:analogs & derivatives* / Q000138:chemical synthesis* / Q000737:chemistry
D000498:Allyl Compounds; D007659:Ketones; D063065:Organophosphonates; D012717:Sesquiterpenes; C078098:ar-turmerone; D014050:Toluene; D010165:Palladium