Catalytic processes for selective organic synthesis are described. Organolanthanides, group 3 organometallics, and group 4 cationic complexes will be utilized as catalysts in a wide range of processes for the construction of complex organic molecules from rather simple, readily available precursors. A family of organometallic complexes will be synthesized exhibiting significant reactivity, selectivity, and catalytic turnover in the processes outlined. This requires substantial """"""""tuning"""""""" of the metal, the ligand, and, in the case of cationic complexes, the counterion of the catalyst. Processes to be developed are expected to exhibit a high degree of regioselectivity and diastereoselectivity. A long-term objective will be to develop chiral, nonracemic catalysts for use in asymmetric synthesis of organic molecules. At the outset, the chemistry to be carried out will be focused on fundamental aspects of the new synthetic methods. However, ready access to compounds generated by these methods will provide more efficient and economical means to biologically active materials of interest to the pharmaceutical industry. For example, the reactions can be sequenced to provide a dramatic increase in molecular complexity from simple starting materials to the final products. Furthermore, the methods are environmentally sound in that they proceed in a manner where no byproducts are generated (i.e., they proceed with """"""""atom economy""""""""). Several diverse areas, all catalyzed by the same class of organometallics, have been targeted for study. These include: 1) Hydrosilylation and hydroboration reactions. 2) Silylmetalation reactions. 3) Olefin amination reactions. 4) Cyclization reactions of polyolefins, dieneynes, enediynes, etc. involving sequential reactions wherein the cyclizations are terminated by silylation, boration, hydrogenolysis, or beta-hydride elimination.
| Molander, Gary A; Canturk, Belgin (2009) Organotrifluoroborates and monocoordinated palladium complexes as catalysts--a perfect combination for Suzuki-Miyaura coupling. Angew Chem Int Ed Engl 48:9240-61 |
