balt-catalysed Isomerisation reactions of double bonds

该项目涉及通过钴催化剂选择性异构化（官能化）末端烯烃、1，3-二烯和α，ω-二烯中的双键，遵循迄今未知的反应机理，消除了其他催化剂的一些限制和问题。Ph 2 PH配体在所提出的中间体中起重要作用，所述中间体从磷原子递送氢，而不是从金属氢化物中间体递送氢，如对于许多其他异构化催化剂所提出的，导致总的1，3-氢转移反应。结合前述的1，5-氢转移反应，我们将能够从简单的起始原料产生具有2 E，4 Z-、2 Z，4 E-和2 Z，4 Z-双键构型的信息素型产物。将1，3-氢转移反应应用于官能化的末端烯烃和1，6-二烯，可以生成高功能密度的结构单元，这将对有机合成做出巨大贡献。动力学拆分将通过1，3-氢移位产生手性产物，并且迄今未知的α，ω-二烯的去对称化将产生具有季立体中心的手性结构单元。在产物中引入官能团将导致产物具有进一步应用的高合成潜力。

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.