期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 58, 期 9, 页码 2795-2798出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201814362
关键词
axial chirality; counterion; energy transfer; phase transfer; visible light
资金
- EPSRC [EP/R005826/1]
- EPSRC Centre for Doctoral Training in Synthesis for Biology and Medicine [EP/L015838/1]
- People Programme (Marie Curie Actions) of the European Union's Seventh Framework Programme for funding (FP7/2007-2013, REA) [316955]
- Agency for Science, Technology and Research (A*STAR) Singapore
- EPSRC [EP/R005826/1] Funding Source: UKRI
Non-biaryl atropisomers are valuable in medicine, materials, and catalysis, but their enantioselective synthesis remains a challenge. Herein, a counterion-mediated O-alkylation method for the generation of atropisomeric amides with an er up to 99:1 is outlined. This dynamic kinetic resolution is enabled by the observation that the rate of racemization of atropisomeric naphthamides is significantly increased by the presence of an intramolecular O-H center dot center dot center dot NCO hydrogen bond. Upon O-alkylation of the H-bond donor, the barrier to rotation is significantly increased. Quantum calculations demonstrate that the intramolecular H-bond reduces the rotational barrier about the aryl-amide bond, stabilizing the planar transition state for racemization by approximately 40 kJ mol(-1), thereby facilitating the observed dynamic kinetic resolution.
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