Benzannulation of Triynes to Generate Functionalized Arenes by Spontaneous Incorporation of Nucleophiles
Benzannulation of Triynes to Generate Functionalized Arenes by Spontaneous Incorporation of Nucleophiles
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三炔苯并环化通过亲核试剂的自发掺入生成功能化芳烃
DOI：
10.1002/anie.201412468
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发表时间：
2015-05-26
影响因子：
16.6
通讯作者：
Lee, Daesung
中科院分区：
文献类型：
--
作者：
Karmakar, Rajdip;Yun, Sang Young;Lee, Daesung
酯键连的1，3，8-三炔的热反应提供了伴随引入亲核试剂的新型苯并环化产物。有证据表明，该反应通过在第一步中由Alder烯反应产生的丙二烯-烯炔中间体进行。取决于丙二烯-烯炔中间体上的炔部分的取代基，随后的转化可以采取两种不同路径中的一种，每种路径导致离散的芳构化产物。硅烷取代的1，3，8-三炔的苯甲酰化提供了具有结合到新形成的苯核上的亲核试剂的芳烃产物，而芳基取代基导致亲核试剂在连接到芳基取代基的苄基碳原子处捕获。这两种不同产物的形成是由于两种区域异构的丙二烯-烯炔中间体的参与。
The thermal reaction of ester-tethered 1,3,8-triynes provides novel benzannulation products with concomitant incorporation of a nucleophile. Evidence suggests that this reaction proceeds via an allene-enyne intermediate generated by an Alder-ene reaction in the first step. Depending on the substituent of the alkyne moiety on the allene-enyne intermediate, the subsequent transformation can take one of two different paths, each leading to discrete aromatization products. The benzannulation of a silane-substituted 1,3,8-triynes provides arene products with a nucleophile incorporated onto the newly formed benzene core, whereas an aryl substituent leads to nucleophile trapping at the benzylic carbon atom connected to the aryl substituent. The formation of these two different products results from the involvement of two regioisomeric allene-enyne intermediates.