Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13, 81377 München, Germany.
Chemistry. 2011 Apr 4;17(15):4232-7. doi: 10.1002/chem.201003273. Epub 2011 Mar 7.
Readily available 1,1-dichloro-2-alkynes are versatile starting materials for the synthesis of polyfunctionalized allenes. They can be prepared from commercially available terminal alkynes in a two-step procedure. The Cu-mediated reaction of several 1,1-propargylic derivatives with functionalized alkyl, benzylic, or allylic zinc reagents proceeds exclusively with S(N)2' selectivity and allows a rapid and efficient synthesis of functionalized chloroallenes. These chloroallenes undergo a novel Cu(I) -catalyzed substitution reaction with functionalized arylmagnesium reagents with excellent S(N)2 selectivity to give trisubstituted polyfunctionalized allenes. The functional group tolerance is excellent and functionalities, such as cyano, keto, ester, phosphate, trifluoromethyl, and halogens, are well tolerated.
readily available 1,1-dichloro-2-alkynes 是合成多官能化丙二烯的多功能起始材料。它们可以通过两步法从商业上可得的末端炔烃制备。几种 1,1-丙炔基衍生物与功能化的烷基、苄基或烯丙基锌试剂的 Cu 介导反应具有 S(N)2' 选择性，允许快速有效地合成功能化的氯丙二烯。这些氯丙二烯与功能化的芳基镁试剂发生新型 Cu(I)催化取代反应，具有优异的 S(N)2 选择性，得到三取代的多官能化丙二烯。官能团的耐受性非常好，例如氰基、酮基、酯基、磷酸酯基、三氟甲基和卤素等都能很好地耐受。
