Ichikawa Junji, Fukui Hiroki, Ishibashi Yuichiro
Department of Chemistry, Graduate School of Science, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
J Org Chem. 2003 Oct 3;68(20):7800-5. doi: 10.1021/jo034718j.
Various 1,1-difluoro-1-alkenes such as monosubstituted 1,1-difluoro-1-alkenes, 2-bromo-1,1-difluoro-1-alkenes, and 3,3-difluoroallylic alcohols are synthesized in two simple steps from 1-trifluoromethylvinylsilane: (i) its SN2' reaction with nucleophiles to construct 2,2-difluorovinylsilanes and (ii) the subsequent substitution of electrophiles for the vinylic silyl group. The combination of these two processes allows a one-pot synthesis of the functionalized 1,1-difluoro-1-alkenes starting from 1-trifluoromethylvinylsilane, which functions as a CF2=C(-)-CH2+ synthon.
各种1,1 - 二氟 - 1 - 烯烃，如单取代的1,1 - 二氟 - 1 - 烯烃、2 - 溴 - 1,1 - 二氟 - 1 - 烯烃和3,3 - 二氟烯丙醇，可通过两个简单步骤从1 - 三氟甲基乙烯基硅烷合成：（i）其与亲核试剂的SN2'反应以构建2,2 - 二氟乙烯基硅烷，以及（ii）随后用亲电试剂取代乙烯基硅烷基。这两个过程的结合使得能够从1 - 三氟甲基乙烯基硅烷开始一锅法合成官能化的1,1 - 二氟 - 1 - 烯烃，1 - 三氟甲基乙烯基硅烷作为CF2 = C(-)-CH2+合成子。
