Angewandte Chemie International Edition · 2015 · 220 citations · 34 references
Natural SciencesChemistryCatalysisComputational ChemistryOrganic ChemistryCarbonyl ChemistryCatalyst CharacterizationCatalyst DesignCatalytic MaterialsCatalytic MechanismsOrganic SynthesisCatalyst Structure - Activity RelationshipsCatalytic ActivityHydride FormationLewis AcidityMetal HydridesReaction Mechanism ElucidationTransition Metal-catalyzed SynthesisTransition-metal-catalyzed Functionalization
The reaction of [LAlH2 ] (L=HC(CMeNAr)2 , Ar=2,6-iPr2 C6 H3 ) with MeOTf (Tf=SO2 CF3 ) resulted in the formation of [LAlH(OTf)] (1) in high yield. The triflate substituent in 1 increases the positive charge at the aluminum center, which implies that 1 has a strong Lewis acidic character. The excellent catalytic activity of 1 for the hydroboration of organic compounds with carbonyl groups was investigated. Furthermore, it was shown that 1 effectively initiates the addition reaction of trimethylsilyl cyanide (TMSCN) to both aldehydes and ketones. Quantum mechanical calculations were carried out to explore the reaction mechanism.
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Main-group elements as transition metals
Philip P. Power · Nature · 2010 · 1.7K citations
Natural Sciences, Materials Engineering, Materials Science +14