Chiba Shunsuke, Wang Yi-Feng, Lapointe Guillaume, Narasaka Koichi
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore.
Org Lett. 2008 Jan 17;10(2):313-6. doi: 10.1021/ol702727j. Epub 2007 Dec 23.
Two synthetic methods for tetra- and trisubstituted N-H pyrroles are presented: (i) the thermal pyrrole formation by the reaction of vinyl azides with 1,3-dicarbonyl compounds via the 1,2-addition of 1,3-dicarbonyl compounds to 2H-azirine intermediates generated in situ from vinyl azides; (ii) the Cu(II)-catalyzed synthesis of pyrroles from alpha-ethoxycarbonyl vinyl azides and ethyl acetoacetate through the 1,4-addition reaction of the acetoacetate to the vinyl azides. By applying these two methods, regioisomeric pyrroles can be prepared selectively starting from the same vinyl azides.
介绍了两种合成四取代和三取代N-H吡咯的方法：(i) 通过乙烯基叠氮化物与1,3-二羰基化合物反应，经1,3-二羰基化合物对由乙烯基叠氮化物原位生成的2H-氮杂环丙烷中间体进行1,2-加成，热形成吡咯；(ii) 通过α-乙氧羰基乙烯基叠氮化物与乙酰乙酸乙酯经乙酰乙酸乙酯对乙烯基叠氮化物的1,4-加成反应，由铜(II)催化合成吡咯。通过应用这两种方法，可以从相同的乙烯基叠氮化物选择性地制备区域异构体吡咯。
