Regioselective Ring Expansion of 2,4-Diiminoazetidines via Cleavage of C-N and C(sp3)-H Bonds: Efficient Construction of 2,3-Dihydropyrimidinesulfonamides
Regioselective Ring Expansion of 2,4-Diiminoazetidines via Cleavage of C-N and C(sp3)-H Bonds: Efficient Construction of 2,3-Dihydropyrimidinesulfonamides
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DOI：
10.1021/ja211486f
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发表时间：
2012-02-15
影响因子：
15
通讯作者：
Xi, Zhenfeng
中科院分区：
文献类型：
--
作者：
Wang, Yang;Chi, Yue;Xi, Zhenfeng
首次通过 C-N 和 C(sp(3))-H 键的裂解实现了 2,4-二亚氨基氮杂环丁烷的高度区域选择性碱介导环扩张，从而有效地提供了 2,3-二氢嘧啶磺酰胺。两个关键中间体的捕获实验和氘标记研究充分证实了通过串联4 pi 电环开环/1,5-H 位移/6 pi 电环闭环进行扩环的机制。
A highly regioselective base-mediated ring expansion of 2,4-diiminoazetidines via cleavage of C-N and C(sp(3))-H bonds is achieved for the first time to afford efficiently 2,3-dihydropyrimidinesulfonamides. The mechanism of the ring expansion via tandem 4 pi electrocyclic ring-opening/1,5-H shift/6 pi electrocydic ring-closing is well confirmed by the trapping experiments of two key intermediates and deuterium labeling studies.