Stereoselective synthesis of epi-jasmonic acid, tuberonic acid, and 12-oxo-PDA.
epi-Jasmonic acid (epi-JA) and tuberonic acid (TA) were synthesized from the key aldehyde, all cis-2-(2-hydroxy-5-vinylcyclopentyl)acetaldehyde (14), which was in turn prepared stereoselectively from the (1R)-acetate of 4-cyclopentene-1,3-diol (10) through S(N)2-type allylic substitution with CH(2)[double bond, length as m-dash]CHMgBr followed by Mitsunobu inversion, Eschenmoser-Claisen rearrangement, and regioselective Swern oxidation of the corresponding bis-TES ether (13). Wittig reaction of the aldehyde 14 with [Ph(3)P(CH(2))Me](+)Br(-) followed by oxidation afforded epi-JA (3) stereoselectivity over the trans isomer. Similarly, TA (5) was synthesized. Furthermore, the above findings were applied successfully to improve the total efficiency of the previous synthesis of 12-oxo-PDA (1).
Nonaka
Hisato
H
Department of Biomolecular Engineering, Tokyo Institute of Technology, B52, Nagatsuta-cho 4259, Midori-ku, Yokohama 226-8501, Japan. ykobayas@bio.titech.ac.jp.
Ogawa
Narihito
N
Maeda
Noriaki
N
Wang
Yong-Gang
YG
Kobayashi
Yuichi
Y
D000085:Acetates / Q000138:chemical synthesis* / Q000737:chemistry*; D000447:Aldehydes / Q000737:chemistry; D003517:Cyclopentanes / Q000138:chemical synthesis* / Q000737:chemistry*; D005231:Fatty Acids, Unsaturated / Q000138:chemical synthesis* / Q000737:chemistry*; D007783:Lactones / Q000737:chemistry; D054883:Oxylipins / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism; D017962:alpha-Linolenic Acid / Q000737:chemistry / Q000378:metabolism
D000085:Acetates; D000447:Aldehydes; D003517:Cyclopentanes; D005231:Fatty Acids, Unsaturated; D007783:Lactones; D054883:Oxylipins; D017962:alpha-Linolenic Acid; C421182:tuberonic acid; C025999:12-oxophytodienoic acid; C011006:jasmonic acid