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过渡金属催化的碳亲核试剂对氧/氮杂苯并降冰片烯的开环反应是合成氢化萘衍生物的有效方法之一.在该类反应中,采用末端炔烃作为碳亲核试剂在反应操作、底物适用范围等多个方面都具有已报道的各种有机金属亲核试剂所不具备的优势.目前,对末端炔烃与氧/氮杂苯并降冰片烯的开环反应的研究进展有限,只有Ni(dppe)Cl2/ZnCl2/Zn和手性的Rh两种催化体系被应用到该类反应当中,但都面临一些不足.为该类反应开发简单有效的新型催化体系仍然具有重要的意义和价值.我们通过研究发现:PdCl2与Xantphos的配合物是芳基乙炔对氧/氮杂苯并降冰片烯亲核开环反应的有效催化剂.在优化后的反应条件下,该Pd催化剂具有良好的催化活性和底物适应能力,能够实现各种取代的芳基乙炔对氧/氮杂苯并降冰片烯的亲核加成,并以较好的收率生成目标开环产物.
Ring opening of oxygen / azabenzor norbornenes by transition metal-catalyzed carbon nucleophiles is one of the most efficient ways to synthesize naphthalene derivatives.In this type of reaction, terminal alkynes are used as carbon nucleophiles Reaction operations, the scope of the substrate and other aspects have reported the advantages of various organometallic nucleophiles not available.At present, the terminal alkyne and oxygen / azabenzopropenyl ring-opening reaction The research progress is limited, and only two kinds of catalytic systems, Ni (dppe) Cl2 / ZnCl2 / Zn and chiral Rh, are applied to this kind of reaction, but they all face some shortcomings.The new simple and effective catalytic system for this kind of reaction still has Important significance and value.We found through the study: PdCl2 and Xantphos complex is aryl acetylene oxygen / aza-norbornene nucleophilic ring-opening reaction of the catalyst.After the optimized reaction conditions, the Pd The catalyst has good catalytic activity and substrate adaptability, and can realize nucleophilic addition of various substituted aryl acetylenes to oxy / azabenzor norbornene, and produces the target ring-opened product with good yield.