Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 58, Issue 4, Pages 1088-1093Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201811927
Keywords
amination; asymmetric catalysis; azides; chiral-at-metal complexes; ruthenium catalysis
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Funding
- Deutsche Forschungsgemeinschaft [ME 1805/15-1]
- National Science Foundation [CHE-1059084, OCI-1053575]
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An enantioselective ring-closing C(sp(3))-H amination of 2-azidoacetamides is catalyzed by a chiral-at-metal ruthenium complex and provides chiral imidazolidin-4-ones in 31-95 % yield, with enantioselectivities of up to 95 % ee, and at catalyst loadings down to 0.1 mol % (turnover number (TON)=740). To our knowledge, this is the first example of a highly enantioselective C(sp(3))-H amination with aliphatic azides. Mechanistic experiments reveal the importance of the amide group, which presumably enables initial bidentate coordination of the 2-azidoacetamides to the catalyst. DFT calculations show that the transition state leading to the major enantiomer features a better steric fit and favorable pi-pi stacking between the substrate and the catalyst framework.
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