Polymer-supported l-prolinol-based catalysts for the enantioselective addition of dialkylzinc reagents to N-(diphenylphosphinyl)imines

l-Prolinol-based ligands anchored to Merrifield or Wang-type resins have been shown to form efficient catalysts for the enantioselective addition of dialkylzinc reagents to N-(diphenylphosphinyl)imines. The enantioselectivity achieved with the polymeric catalyst (ee up to 88%) is slightly lower than the one obtained with the homogeneous ligand N-benzyl-l-prolinol, but the polymer-supported ligand presents the advantage of its recyclability: it can be recovered and used in up to six consecutive catalytic cycles with only a slight decrease in the enantiomeric excess. The phosphinamides obtained as addition products can be transformed into the corresponding enantiomerically enriched α-branched primary amines under mild acidic conditions.

This work was generously supported by the Spanish Ministerio de Ciencia e Innovación (MICINN; grant no. CONSOLIDER INGENIO 2010, CSD2007-00006, CTQ2007-65218 and CTQ11-24151) and the Generalitat Valenciana (PROMETEO/2009/039, FEDER and GV/2007/036). R.A. thanks the Spanish Ministerio de Educación y Ciencia for a predoctoral fellowship. J.F.C. thanks the Instituto de Síntesis Orgánica for a fellowship.