balt-catalysed Isomerisation reactions of double bonds

该项目致力于通过钴催化(官能化的)端烯、1，3-二烯和α，omega-二烯中的双键选择性异构化，遵循一种迄今未知的反应机理，消除了其他催化剂观察到的一些限制和问题。Ph2Ph配体在所提出的中间体中起着重要的作用，该中间体从磷原子而不是从金属氢化物中间体传递氢，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传递氢，从而导致整个1，3-氢变换反应。与前面描述的1，5-氢变换反应相结合，我们将能够从简单的起始原料中生成具有2E，4Z-，2Z，4E-和2Z，4Z-双键构型的信息素类型的产物。1，3-氢变换反应将应用于功能化的端烯和1，6-二烯，生成具有高功能密度的构筑块，这将对合成有机化学做出重大贡献。动力学拆分将通过1，3-氢位移和迄今未知的α-去对称化生成手性产物，欧米伽-二烯将生成具有四元立体中心的手性构建块。产品中官能团的引入将使产品具有很高的合成潜力，具有进一步的应用前景。

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.