Zhao Yingying, Wang Haolong, Li Xincheng, Wang Dongping, Xin Xiaoyi, Wan Boshun
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China.
Org Biomol Chem. 2016 Jan 14;14(2):526-541. doi: 10.1039/c5ob01887k.
2-Trifluoromethyl-5-(arylsulfonyl)methyl pyrroles and 2-trifluoromethyl-4-(arylsulfonyl)methyl pyrroles were selectively synthesized from trifluoromethyl-substituted 3-aza-1,5-enynes via a cyclization/sulfonyl group migration cascade catalyzed by AgOOCCF3 and CsOPiv, respectively. Alkylvinyl-substituted pyrroles were generated from seven-atom skeleton 3-aza-1,5-enynes via aryl sulfinic acid elimination in the presence of Cs2CO3. Two ion-pair intermediates were proposed and a key intermediate, aza-diene-yne, was successfully isolated in the mechanistic studies.
2-三氟甲基-5-（芳基磺酰基）甲基吡咯和2-三氟甲基-4-（芳基磺酰基）甲基吡咯分别由三氟甲基取代的3-氮杂-1,5-烯炔通过分别由AgOOCCF3和CsOPiv催化的环化/磺酰基迁移级联反应选择性合成。烷基乙烯基取代的吡咯由七原子骨架的3-氮杂-1,5-烯炔在Cs2CO3存在下通过芳基亚磺酸消除反应生成。提出了两种离子对中间体，并在机理研究中成功分离出关键中间体氮杂二烯-炔。
