Artículo
Rhodium phosphine-phosphite catalysts in the hydrogenation of challenging N-(3,4-dihydronaphthalen-2-yl) amide derivatives
Autor/es | Arribas Nieto, Inmaculada
Rubio Moreno, Miguel Kleman, Patryk Artur Pizzano Mancera, Antonio |
Fecha de publicación | 2013 |
Fecha de depósito | 2018-02-15 |
Publicado en |
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Resumen | The enantioselective catalytic hydrogenation of N-(3,4-dihydronaphthalen-2- yl) amides (1) with rhodium catalysts bearing phosphine-phosphite ligands 4 has been studied. A wide catalyst screening, facilitated by the modular ... The enantioselective catalytic hydrogenation of N-(3,4-dihydronaphthalen-2- yl) amides (1) with rhodium catalysts bearing phosphine-phosphite ligands 4 has been studied. A wide catalyst screening, facilitated by the modular structure of 4, has found a highly enantioselective catalyst for this reaction. This catalyst gives a 93% ee in the hydrogenation of 1a and also produces high enantioselectivities, ranging from 83 to 93% ee, in the hydrogenation of several OMe- and Br-substituted substrates. In contrast, the structurally related enol esters 2 are very reluctant to undergo hydrogenation. A coordination study of the representative enamide 1d has shown an unusual η6-arene coordination mode, over the typical O,C,C chelating mode for enamides, as the preferred one for this substrate in a Rh(I) complex. Deuteration reactions of 1c,d indicate a clean syn addition of deuterium to the double bond without an isotopic effect on the enantioselectivity. |
Agencias financiadoras | Ministerio de Ciencia e Innovación (MICIN). España Junta de Andalucía |
Identificador del proyecto | CTQ2009-11867
CSD2007-00006 2008/FQM-3830 2009/FQM-4832 |
Cita | Arribas Nieto, I., Rubio Moreno, M., Kleman, P.A. y Pizzano Mancera, A. (2013). Rhodium phosphine-phosphite catalysts in the hydrogenation of challenging N-(3,4-dihydronaphthalen-2-yl) amide derivatives. Journal of Organic Chemistry, 78, 3997-4005. |
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