Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 19, Issue 8, Pages 2776-2783Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201203190
Keywords
homogeneous catalysis; hydroboration; imines; magnesium; main group elements
Categories
Funding
- EPSRC (UK)
- EPSRC [EP/I014519/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/I014519/1] Funding Source: researchfish
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The -diketiminato magnesium alkyl complex [LMgnBu] (L=CH{CMe(NDipp)}2, Dipp=diisopropylphenyl) is shown to be a highly effective precatalyst for the hydroboration of alkyl and aryl substituted aldimines and ketimines with pinacol borane (HBpin). Catalysis is proposed to occur through a sequence of MgN/BH metathesis and rate-determining MgH/NC insertion steps, a proposal strongly supported by stoichiometric studies and kinetic analysis. The reactions are observed to proceed through the intermediacy of well-defined magnesium amides, two examples of which have been isolated and structurally characterized. Mechanistic investigations suggest that the catalytic rate-determining process occurs at an isolated magnesium center and requires the presence of two molecules of the imine substrate for effective turnover. This latter observation is rationalized as a requirement for the secondary substrate molecule to displace HBpin from the coordination sphere of the catalytic magnesium center.
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