Kawasaki T, Nonaka Y, Watanabe K, Ogawa A, Higuchi K, Terashima R, Masuda K, Sakamoto M
Meiji Pharmaceutical University, 2-522-1, Noshio, Kiyose, Tokyo 204-8688, Japan.
J Org Chem. 2001 Feb 23;66(4):1200-4. doi: 10.1021/jo0014921.
The reverse aromatic Cope rearrangement of 2-allyl-3-alkylideneindolines obtained by Horner-Wadsworth-Emmons olefination of 2-allylindolin-3-ones was performed. When 2-allylindolin-3-ones were treated with phosphonium ylides in refluxing toluene, domino Wittig reaction and reverse aromatic Cope rearrangement took place to give alpha-allyl-3-indole acetate derivatives in good yields. The aromatization as a new driving force in the Cope rearrangement is preferable to the conjugation with the carbonyl and cyano groups and also to the alkyl substitution pattern, which are well-known driving forces.
通过2-烯丙基吲哚-3-酮的霍纳-沃兹沃思-埃蒙斯烯烃化反应得到的2-烯丙基-3-亚烷基吲哚啉进行了逆芳香族科普重排反应。当2-烯丙基吲哚-3-酮在回流甲苯中与鏻叶立德反应时，发生多米诺维蒂希反应和逆芳香族科普重排反应，以良好的产率得到α-烯丙基-3-吲哚乙酸酯衍生物。作为科普重排反应中新驱动力的芳构化作用优于与羰基和氰基的共轭作用以及烷基取代模式，而后两者是众所周知的驱动力。
