Research GroupsKirschning Group
Research -Methodology (SynMeth)

The chemistry of hypervalent halides

In the years 1998 and 1999 we reported on the preparation of a new class of electrophilic halonium reagents, which are obtained by iodine(III)-mediated oxidation of bromide and iodide. The resulting haloate(I)-complexes can be further diversified by ligand exchange. These reagents show a large synthetic versatility.  

with G. Sourkouni-Argirusi, Org. Lett. 2000, 2, 3781-3784.

with S. Luiken, J. Org. Chem. 2008, 73, 2018-2020.

with H. Monenschein et al. Angew. Chem. 1999, 111, 2720-2722.

with J. Jaunzems, Angew. Chem.  Int. Ed. 2003, 42, 1166-1170.

OXIDATIVE DECARBONYLATION OF ALDEHYDES

The stereocontrolled palladium catalyzed umpolung allylation utilizes diboranes to yield intermediate allylboranes that directly react with aldehydes. Stereocontrol is best achieved when chiral aldehydes are employed. with A. Kipke, K.-U. Schöning Eur. J. Org. Chem. 2017, 46, 6906–6913.

ASYMMETRIC FORMYLATION OF ALDEHYDES

Our concept of the asymmetric formylation of aldehydes is based on dissecting the C-C bond forming process and the establishment of the newly formed stereogenic center. This is achieved by Horner-Wittig olefination of the aldehyde followed by Sharpless asymmetric dihydroxylation of the intermediate O,O-ketene acetal. with G. Dräger & A. Jung, Angew. Chem. 1997, 109, 253-255. with H. Monenschein, et al. Chem. Eur. J. 1999, 5, 2270-2280.