Kim Mansuk, Lee Daesung
Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, USA.
J Am Chem Soc. 2005 Dec 28;127(51):18024-5. doi: 10.1021/ja057153c.
We have demonstrated that the combined use of enyne metathesis and metallotropic [1,3]-shift of the corresponding alkynyl ruthenium carbenes is a powerful synthetic tool to construct oligoenynes. In this reaction, alkynyl carbene intermediates formed from an initial ring-closing metathesis reaction (RCM) undergo repetitive [1,3]-shifts and RCMs to give the final products. Linear poly-1,3-diynes containing repeating functionality of the type -[XCH2CCCCCH2]n- generated long-chain conjugated oligoenynes up to n = 5.
我们已经证明,烯炔复分解反应与相应炔基钌卡宾的金属otropic [1,3]-迁移相结合是构建低聚烯炔的有力合成工具。在该反应中,由初始闭环复分解反应(RCM)形成的炔基卡宾中间体经历重复的[1,3]-迁移和RCM反应以得到最终产物。含有-[XCH2CCCCCH2]n-类型重复官能团的线性聚-1,3-二炔生成了长达n = 5的长链共轭低聚烯炔。