A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences , 1 Favorsky Str., 664033 Irkutsk, Russia.
Org Lett. 2017 Jun 16;19(12):3127-3130. doi: 10.1021/acs.orglett.7b01254. Epub 2017 May 26.
The products of the one-pot assembly of acetylene and ketones in the KOH/DMSO system, 7-methylene-6,8-dioxabicyclo[3.2.1]octanes, undergo an acid-catalyzed (CFCOOH, room temperature) rearrangement to rarely substituted cyclopentadienes in good-to-excellent yields. The mechanism of the rearrangement has been supported by the isolation and corresponding transformations of two intermediates.
在 KOH/DMSO 体系中，乙炔和酮的一锅法组装产物 7-亚甲基-6,8-二氧杂双环[3.2.1]辛烷，经酸催化（CFCOOH，室温）重排，以良好至优异的收率得到很少取代的环戊二烯。该重排反应的机理得到了两种中间体的分离和相应转化的支持。
