Department of Biomolecular Engineering, Tokyo Institute of Technology, B52, Nagatsuta-cho 4259, Midori-ku, Yokohama 226-8501, Japan.
Org Biomol Chem. 2010 Nov 21;8(22):5212-23. doi: 10.1039/c0ob00218f. Epub 2010 Sep 16.
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))MeBr(-) 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).
表茉莉酸（epi-JA）和块马尿酸（TA）由关键醛基，全顺式-2-（2-羟基-5-乙烯基环戊基）乙醛（14）合成，而 14 又可以从（1R）-4-环戊烯-1,3-二醇（10）的乙酸酯立体选择性地制备，方法是通过 CH(2)[双键，长度为破折号]CHMgBr 进行 S(N)2 型烯丙基取代，然后进行 Mitsunobu 反转、Eschenmoser-Claisen 重排以及相应的双-TES 醚（13）的区域选择性 Swern 氧化。醛 14 与Ph(3)P(CH(2))MeBr(-)的 Wittig 反应，然后氧化，得到表茉莉酸（3），其对反式异构体具有立体选择性。类似地，合成了 TA（5）。此外，上述发现成功应用于改进 12-氧代-PDA（1）的先前合成的总效率。
