Organo- and Iron(0) Catalysis for an Enantioselective Michael Addition-Hemiketalization-Fragmentation Sequence to Protected omega-Hydroxy-nitroketones

Adrien Quintard (1) , Jean Rodriguez (1)

1 ISM2 - Institut des Sciences Moléculaires de Marseille

By combining an organocatalyzed Michael addition of 1,3-diketones to hydroxy-nitroolefins with a subsequent, innovative iron(0)-catalyzed fragmentation, key enantioenriched ketones possessing additional nitro and protected alcohol functions could efficiently be prepared under excellent enantiocontrol (typically 95% ee). The reaction was made possible by the discovery that photochemical activation of iron pentacarbonyl [Fe(CO)5], a cheap widely available complex, efficiently catalyzed a Claisen-type fragmentation under mild conditions, avoiding decomposition of the intermediates and products.

Mots clés: enantioselective synthesis; fragmentation; homogeneous catalysis; iron(0) catalysis; organocatalysis

Domaines: Chimie organique

Adrien Quintard, Jean Rodriguez. Organo- and Iron(0) Catalysis for an Enantioselective Michael Addition-Hemiketalization-Fragmentation Sequence to Protected omega-Hydroxy-nitroketones. Advanced Synthesis and Catalysis, 2016, 358, pp.3362. ⟨10.1002/adsc.201600618⟩. ⟨hal-01415034⟩