Dichlorination of (hexadehydro-Diels-Alder generated) benzynes and a protocol for interrogating the kinetic order of bimolecular aryne trapping reactions.

Dichlorination of (hexadehydro-Diels-Alder generated) benzynes and a protocol for interrogating the kinetic order of bimolecular aryne trapping reactions.
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DOI:
10.1021/ol403258c
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发表时间:
2014-01-03
期刊:
影响因子:
5.2
通讯作者:
Hoye, Thomas R.
Hoye, Thomas R.
中科院分区:
化学1区
文献类型:
--
作者:
Niu, Dawen;Wang, Tao;Woods, Brian P.;Hoye, Thomas R.

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报道了由六氢Diels-Alder(HDDA)反应制备的苯乙炔的高效二氯化反应。在四氯铜酸二锂存在下,三炔底物的环异构化反应通过捕获苯炔中间体得到二氯化产物A。提出了一种识别外部芳烃捕捉剂动力学级数的一般策略。它只需要测量双分子与单分子捕获事件之间的竞争(这里,二氯化与IMDA反应分别得到A与B)作为捕捉剂浓度的函数。
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. IMDA reaction to give A vs. B, respectively) as a function of the concentration of the trapping agent.
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发表时间: 2014-01
期刊: Nature chemistry
影响因子: 21.8
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