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Abstract:
Selective introduction of methyl branches into the carbon chains of alcohols can be achieved with low loadings of ruthenium precatalyst [RuH(CO)(BH4)(HN(C2H4PPh2)(2))] (Ru-MACHO-BH) using methanol both as methylating reagent and as reaction medium. A wide range of structurally divers alcohols was beta -methylated with excellent selectivity (>99%) in fair to high yields (up to 94%) under standard conditions, and turnover numbers up to 18,000 could be established. The overall reaction rate of the complex catalytic network appears to be governed by interconnection of the individual subcycles through availability of the reactive intermediates. The synthetic procedure opens pathways to important structural motifs following the Green Chemistry principles.
