balt-catalysed Isomerisation reactions of double bonds

• Applicant: Professor Dr. Gerhard Hilt
• Subject Area: Organic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2015 to 2020
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 266161993

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.

• DFG Programme: Research Grants