Angewandte Chemie International Edition · 2011 · 79 citations · 40 references
Natural SciencesChemistryCatalysisOrganic ChemistryOrganometallic ChemistryCatalytic MechanismsSelectivity OptimizationAlkylation ReactionsAlkyne ActivationLigand DesignLigand-controlled Selectivity
It's all in the ligand: By choice of the appropriate diphosphine ligand a previously linear-selective alkyne hydroacylation process can be “switched” to be highly branched-selective (see scheme, l=linear, b=branched). Structural data for the ortho-iPr-dppe–rhodium catalyst suggest restricted rotation of the phosphine aryl units may be responsible for the observed selectivity.
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Fumitoshi Shibahara, John F. Bower, Michael J. Krische · Journal of the American Chemical Society · 2008 · 199 citations · Full text