Department of Chemistry, University of Minnesota , 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.
Org Lett. 2014 Jan 3;16(1):254-7. doi: 10.1021/ol403258c. Epub 2013 Dec 13.
The efficient dichlorination of benzynes prepared by the hexadehydro-Diels-Alder (HDDA) reaction is reported. Cycloisomerization of a triyne substrate in the presence of dilithium tetrachlorocuprate is shown to provide dichlorinated products A by capture of the benzyne intermediate. A general strategy for discerning the kinetic order of an external aryne trapping agent is presented. It merely requires measurement of the competition between bimolecular vs unimolecular trapping events (here, dichlorination vs intramolecular Diels-Alder (IMDA) reaction to give A vs B, respectively) as a function of the concentration of the trapping agent.
报道了通过十六氢化狄尔斯-阿尔德（HDDA）反应制备的苯炔的高效二氯化。在二锂四氯铜的存在下，三炔底物的环异构化被证明可以通过捕获苯炔中间体来提供二氯化产物 A。提出了一种用于确定外部芳炔捕获剂动力学顺序的一般策略。它只需要测量双分子与单分子捕获事件之间的竞争（这里，分别是二氯化与分子内 Diels-Alder（IMDA）反应以分别得到 A 与 B）作为捕获剂浓度的函数。
