期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 21, 期 35, 页码 12488-12500出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201502090
关键词
asymmetric synthesis; bispidine; Henry reaction; polycyclic compounds; stereoselective catalysis
资金
- German Science Foundation (DFG)
The first modular and flexible synthesis of core-chiral bispidines was achieved by using an inside-out strategy. The key intermediate, a NBoc-activated bispidine lactam, was constructed in enantiomerically pure form from a chirally modified beta-amino acid and 2-(acetoxymethyl)acrylonitrile in just five steps and good 48% yield. A simple addition-reduction protocol permitted a highly endo-selective introduction of substituents and, thus, a fast and variable access to 2-endo-substituted and 2-endo, N-fused bi- and tri-cyclic bispidines. The new diamines were evaluated as the chiral ligands in asymmetric Henry reactions. Excellent enantioselectivities of up to 99% ee and good diastereomeric ratios of up to 86: 14 were reached with a copper(II) complex modified by a 2-endo, N-(3,3-dimethylpyrrolidine)-annelated bispidine. Its performance is superior to that of the well-known bispidines (-)-sparteine .and the (+)-sparteine surrogate.
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