期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 78, 期 13, 页码 6510-6521出版社
AMER CHEMICAL SOC
DOI: 10.1021/jo400700m
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资金
- Ministerio de Economia y Competitividad [CTQ2010-21755-CO2-02]
- Junta de Andalucia [P07-FQM-2774]
- Ministerio de Asuntos Exteriores y de Cooperacion
The application of acyclic C-2-symmetric chelating bis-sulfoxide ligands in the Rh(I)-catalyzed enantioselective 1,4-addition of boronic acids to electron-deficient alkenes is reported. Among the acyclic ethane-bridged bis-sulfoxides tested, the ligand Ferbisox (11), bearing ferrocenyl moieties as substituents at the sulfinyl sulfurs, has exhibited the best results in terms of chemical yield (up to 96%) and enantioselectivity (up to 97% ee). The conjugate addition takes place smoothly in toluene at room temperature in short reaction times (typically 2 h). The reaction scope, including the use of different boronic acids, five-, six-, and seven-membered cyclic enones, an unsaturated lactone, and the most challenging acyclic ketones, is reported. An X-ray diffraction study of the [Ferbisox-RhCl](2) precatalyst clearly exhibits a dimeric structure with an S coordination of the sulfoxide to rhodium. On the basis of the X-ray data and on structural studies conducted in solution by H-1 NMR, a model explaining the high enantioselection observed is proposed.
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