Kobayashi Yusuke
School of Pharmaceutical Sciences, Mukogawa Women's University, Nishinomiya, Hyogo, Japan.
Yakugaku Zasshi. 2011;131(7):1037-46. doi: 10.1248/yakushi.131.1037.
Viridicatin derivatives were synthesized from cyanoacetanilides utilizing the CN groups as electron-withdrawing groups and leaving groups. Also, the key scaffolds of glycocitlones were constructed via the intramolecular Houben-Hoesch-type reactions of cyanoacetanilides where the CN groups functioned as electrophiles. It was found that Houben-Hoesch-type reactions of cyanoacetanilides were promoted by α-functionalization such as perfluoroacylation and N,N-dimethylaminomethylenation and that introduction of such substituents at α-position with respect to the CN groups greatly influenced the physical properties and chemical reactivity of the CN groups.
利用氰基作为吸电子基团和离去基团，从氰基乙酰苯胺合成了绿胶霉素衍生物。此外，通过氰基乙酰苯胺的分子内Houben-Hoesch型反应构建了糖柠檬素的关键骨架，其中氰基作为亲电试剂。研究发现，氰基乙酰苯胺的Houben-Hoesch型反应可通过α-官能化（如全氟酰化和N,N-二甲基氨基亚甲基化）来促进，并且在相对于氰基的α-位引入此类取代基会极大地影响氰基的物理性质和化学反应活性。
