123214-38-0Relevant articles and documents
Syntheses of Chiral 4'-Hydroxy and 1',4'-Dihydroxy-γ-ionylideneacetic Acids, Fungal Biosynthetic Intermediates of Abscisic Acid
Yamamoto, Hiroshi,Oritani, Takayuki,Yamashita, Kyohei
, p. 1923 - 1929 (2007/10/02)
Both chiral 4'-hydroxy and 1',4'-dihydroxy-γ-ionylideneacetic acids (3, 4 and 5), biosynthetic intermediates of abscisic acid produced by Cercospora cruenta, were synthesized from a chiral starting material, (R)- or (S)-4-hydroxy-2,2-dimethyl-1-cyclohexanone (7). -Sigmatropic rearrangement of (S)-1-chloromethyl-3,3-dimethyl-5-tetrahydropyranyl(THP)oxy-1-cyclohexene (8), followed by the Reformatsky reaction with 4-bromo-3-methyl-2-butenoate (10) gave (1'R,4'S)-4.The diastereomeric isomer, (1'R,4'R)-3, was synthesized in the same manner.The reaction of (S)-2,2-dimethyl-5-methylene-4-THPoxy-1-cyclohexanone (14) with a Grignard reagent prepared from (Z)-3-methyl-2-penten-4-ynyl THP ether (15) and subsequent conversion of the side chain gave (1'S,4'S)-5.These synthetic compounds confirmed the stereochemistry of natural 3, 4 and 5.