Synthetic modifications of the natural lignan hydroxymatairesinol towards ligands for asymmetric catalysis

Finland has a long history of utilizing wood as fuel, construction material and for paper production. However, modern reality raises the question of more efficient and advanced utilization of wood‐based natural products. One promising family of compounds are lignans, which are highly abundant in wood knots, especially hydroxymatairesinol (HMR). Having a complex structure and few chirally pure stereocenters, HMR could be used for preparation of valuable fine chemicals. One of the most efficient ways to utilize the complex chiral structure would be as ligands in asymmetric catalysis. Herein the development of asymmetric catalysts based on the structure of HMR is described. In the first part of the thesis, the concept of using hydroxymatairesinol as a starting material for creating asymmetric catalysts as well as molecular modeling to confirm the concept are presented. The second part of this work describes the synthetic modification of hydroxymatairesinol towards chiral diols. A series of chiral diols were prepared and examined as ligands in asymmetric catalytic reactions. Parts 3 and 4 are related to the preparation of phosphorous derivatives. Part 3 is concentrated on H‐phosphonates and phosphates prepared from the chiral diols described in the second part. In part 4, the synthesis of chiral phosphines based on the lignan backbone is described. The applications of the phosphines as ligands in rhodium catalyzed asymmetric hydrogenations are disclosed.