Versatile asymmetric synthesis of the kavalactones: first synthesis of (+)-kavain.
[reaction: see text] Three asymmetric pathways to the kavalactones have been developed. The first method is chiral auxiliary-based and utilizes aldol reactions of N-acetyl thiazolidinethiones followed by a malonate displacement/decarboxylation reaction. The second approach uses the asymmetric catalytic Mukaiyama additions of dienolate nucleophile equivalents developed by Carreira and Sato. Finally, tin-substituted intermediates, prepared by either of these routes, can serve as advanced general precursors of kavalactone derivatives via Pd(0)-catalyzed Stille couplings with aryl halides.
Smith
Thomas E
TE
Department of Chemistry, Williams College, Williamstown, Massachusetts 01267, USA. tsmith@williams.edu
Djang
Mabel
M
Velander
Alan J
AJ
Downey
C Wade
CW
Carroll
Kathleen A
KA
Van Alphen
Sophie
S
D002384:Catalysis; D007202:Indicators and Reagents; D007783:Lactones / Q000138:chemical synthesis*; D009942:Organometallic Compounds / Q000737:chemistry; D010165:Palladium / Q000737:chemistry; D011753:Pyrones / Q000138:chemical synthesis*; D013237:Stereoisomerism; D014001:Tin / Q000737:chemistry
D007202:Indicators and Reagents; D007783:Lactones; D009942:Organometallic Compounds; D011753:Pyrones; D010165:Palladium; D014001:Tin; C011889:kavain