Group XIV.
Asymmetric Synthesis: Alkaloids and Alkaloid-Like Ligands for Metal Based Catalysis
|
Head of the group: Assoc. Prof. Zbigniew Kałuża e-mail: zkicho@icho.edu.pl |
Ph.D., Institute of Organic Chemistry Polish Academy of Sciences, Warsaw, Poland, 1988. Post-doc, Stevens Institute of Technology (SIT), Hoboken, USA, 1989-1991. Habilitation, Institute of Organic Chemistry Polish Academy of Sciences, Warsaw, Poland, 2000. Award of the Division of Mathematics, Physics and Chemistry of the Polish Academy of Sciences, 1997. |
Staff:
Danuta Mostowicz, Ph.D.; Grzegorz Dołęga, Ph.D. student; Rafał Ćwiek, Ph.D. student.
Research activities:
Our research interest is concentrate in two major areas of advanced organic synthesis:
1. Stereoselective synthesis of isoquinoline and pyrrolo[2,1-a]isoquinoline alkaloids that contained a quaternary carbon stereocenter next to the nitrogen atom. We have recently elaborated a new approach to the synthesis of 1,2-dihydroxy-hexahydropyrrolo-isoquinolines and their conversion into highly substituted, optically pure tetrahydro-isoquinolines, new synthons for the preparation of isoquinoline alkaloids. The utility of such synthons was demonstrated by the synthesis of (+)-6,7-dimethoxy-salsoline-1-carboxylic acid and its new 1-phenyl analog.
2. A second area of emphasis is molecular design and synthesis of enantiopure b-aminoalkohols and their application to the asymmetric catalysis. With relation to above project, we selected as our synthetic target β-amio alcohols containing a rigid isoquinoline skeleton and a quaternary carbon stereocenter located in the α-nitrogen position. A simple procedure of preparation of such alcohols was elaborated, as well as their conversion into respective N,N-, N,P-, and P,P- ligands.
All obtained isoquinoline alkaloid-like ligands, are currently applied to enantioselective reactions such as: transfer hydrogenation of ketones, organozinc additions to carbonyl compounds (β-aminoalcohols), palladium catalyzed allylic alkylation (N,P-, P,P-ligants) and desymmetrization of meso-1,2-diols via asymmetric acylation (C2 – symmetrical diamines).
Selected Recent Representative Publication:
1. Kałuża, Z.; Mostowicz, D.; Dołęga, G.; Wójcik, R.: “A New Route to Optically Pure Highly Functionalized Tetrahydro-isoquinolines with a Quaternary Carbon Stereocenter” Tetrahedron. 64, 2008, 2321-2328.
2. Kałuża, Z.; Mostowicz, D.; Dołęga, G.; Mroczko, K.; Wójcik, R.: “10b-Substituted Hexahydropyrrolo-isoquinolines: Studies on Diastereoselective Formation of a Quaternary Carbon Stereocenter via N-Acyliminium Ion Cyclization”, Tetrahedron, 62, 2006, 943-953.
3. D. Mostowicz, R. Wójcik, G. Dołęga, and Z. Kałuża: „Diastereoselective synthesis of 10b-substituted hexahydropyrrolo-isoquinolines from L-tartaric acid. “Creation of a quaternary carbon stereocenter via N-acyliminium ion cyclization” Tetrahedron Letters, 45, 2004, 6011-60015.
4. Z. Kałuża, D. Mostowicz: „Synthesis of enantiopure 1,2-dihydroxyhexahydropyrrolo-isoquinolines as potential tools for asymmetric catalysis” Tetrahedron Asymmetry,14, 2003, 225-232.
