balt-catalysed Isomerisation reactions of double bonds

该项目涉及（功能化）末端烯烃，1,3-二烯和-，- -二烯的双键选择性异构化，通过钴催化，遵循迄今未知的反应机制，消除了其他催化剂观察到的一些限制和问题。Ph2PH配体在提出的中间体中发挥重要作用，从磷原子中传递氢，而不是像许多其他异构化催化剂那样从金属氢化物中间体中传递氢，导致整体1,3-氢移位反应。结合前面描述的1,5-氢移位反应，我们将能够从简单的原料中生成具有2E，4Z-, 2Z，4E-和2Z，4Z-双键构型的信息素型产品。1,3-氢移位反应将应用于功能化末端烯烃和1,6-二烯，生成具有高功能密度的构建单元，这将对合成有机化学做出重大贡献。动力学分解将通过1,3-氢位移产生手性产物，迄今为止未知的- - -二烯的不对称将产生具有四级立体中心的手性构件。在产品中加入官能团将导致具有高合成潜力的产品进一步应用。

The project deals with the selective isomerisation of double bonds in (functionalised) terminal alkenes, 1,3-dienes and alpha,omega-dienes via cobalt catalysis following a hitherto unknown reaction mechanism eliminating some of the restrictions and problems observed with other catalysts. The Ph2PH ligand plays an important role in the proposed intermediate delivering the hydrogen from the phosphorous atom and not from a metal-hydride intermediate as proposed for many other isomerisation catalysts resulting in a overall 1,3-hydrogen shift reaction. In combination with the previously described 1,5-hydrogen shift reaction we will be able to generate pheromone-type products with 2E,4Z-, 2Z,4E- and 2Z,4Z-double bond configuration from simple starting materials. The 1,3-hydrogen shift reaction will be applied to functionalized terminal alkenes and 1,6-dienes to generate building blocks with high functional density which will make a great contribution to synthetic organic chemistry. The kinetic resolution will generate chiral products via a 1,3-hydrogen shift and a hitherto unknown desymmetrisation of alpha,omega-dienes will generate chiral building blocks with quaternary stereogenic centers. The incorporation of functional groups in the products will lead to products with a high synthetic potential for further applications.