The addition of water and methanol to the carbonyl substituents in the dicationic bis(arene)ruthenium complexes [(p-cymene)Ru(C6H5CHO)][OTf]2 (1) and [(p-cymene)Ru(C6H5C(O)CH3)][OTf]2 (2) is remarkably favorable-the equilibrium constants for these reactions are 1 million times greater than those for uncomplexed benzaldehyde and acetophenone. The addition of methanol to the carbonyl group in the o-anisaldehyde complex, [(p-cymene)Ru(C6H4{OCH3}CHO)][OTf]2 (6), occurs with a high degree of kinetic selectivity (94% de).
The N‐(1‐methylbenzyl) or N‐silylphenoxazines (I) are lithiated at C4 or C4 and C6, depending on the amount of butyllithium employed, and then quenched with various electrophiles, e.g. (II) or CO2 (VI), yielding mono‐ and disubstituted derivatives.
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