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Stereodynamic tetrahydrobiisoindole "NU-BIPHEP(O)"s: functionalization, rotational barriers and non-covalent interactions.


ABSTRACT: Stereodynamic ligands offer intriguing possibilities in enantioselective catalysis. "NU-BIPHEPs" are a class of stereodynamic diphosphine ligands which are easily accessible via rhodium-catalyzed double [2 + 2 + 2] cycloadditions. This study explores the preparation of differently functionalized "NU-BIPHEP(O)" compounds, the characterization of non-covalent adduct formation and the quantification of enantiomerization barriers. In order to explore the possibilities of functionalization, we studied modifications of the ligand backbone, e.g., with 3,5-dichlorobenzoyl chloride. Diastereomeric adducts with Okamoto-type cellulose derivatives and on-column deracemization were realized on the basis of non-covalent interactions. Enantioselective dynamic HPLC (DHPLC) allowed for the determination of rotational barriers of ?G (‡) 298K = 92.2 ± 0.3 kJ mol(-1) and 99.5 ± 0.1 kJ mol(-1) underlining the stereodynamic properties of "NU-BIPHEPs" and "NU-BIPHEP(O)s", respectively. These results make the preparation of tailor-made functionalized stereodynamic ligands possible and give an outline for possible applications in enantioselective catalysis.

SUBMITTER: Storch G 

PROVIDER: S-EPMC4979906 | BioStudies | 2016-01-01T00:00:00Z

REPOSITORIES: biostudies

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