Mukai Chisato, Hara Yasuyuki, Miyashita Yusuke, Inagaki Fuyuhiko
Division of Pharmaceutical Sciences, Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan.
J Org Chem. 2007 Jun 8;72(12):4454-61. doi: 10.1021/jo070513p. Epub 2007 May 18.
The simple refluxing of allenynes, having a phenylsulfonyl functionality on the allenyl group, in xylene (or mesitylene) without microwave irradiation resulted in the efficient formation of bicyclo[5.2.0]nona-1,7-dienes and bicyclo[4.2.0]octa-1,6-dienes in high yields. This method was shown to be successfully applicable to the first construction of bicyclo[6.2.0]deca-1,8-dienes. Construction of the corresponding oxa- and azabicyclo[m.2.0] frameworks could also be attained. This thermal ring-closing reaction involves the formal [2+2] cycloaddition in which the distal double bond of an allenyl moiety exclusively served as one of the pi-components regardless of the position of the phenysulfonyl functionality on the allenyl moiety.
在没有微波辐射的情况下，将在烯丙基上具有苯磺酰基官能团的联烯炔在二甲苯（或均三甲苯）中简单回流，能高效地高产率生成双环[5.2.0]壬-1,7-二烯和双环[4.2.0]辛-1,6-二烯。该方法已成功应用于双环[6.2.0]癸-1,8-二烯的首次构建。相应的氧杂和氮杂双环[m.2.0]骨架的构建也能实现。这种热环化反应涉及形式上的[2+2]环加成，其中烯丙基部分的远端双键专门作为π-组分之一，而与苯磺酰基官能团在烯丙基部分上的位置无关。
