Development of a selective hydroxylation, amination and alkylation of prochiral CH2-groups via sequential Ru-catalysis

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In the project a program aiming to develop a system for the selective C-H functionalisation, that is somewhat complementary to the existing procedures, is reported. In contrast to the existing methodologies the functional group will not be part of the oxidizing system but will be introduced using classical carbonyl group transformations. In order to develop this system the basic concept of the hydrogen-autotransfer-catalysis will be combined with a sequential Ru-catalyzed C-H oxidation and reduction. Initially, the cationic (P^N^N^P)Ru(acetonitrile)Cl-complex will be used for the oxidation of a methylene group into a ketone, which will be reduced by the same catalyst under hydrogenation or transferhydrogenation conditions. This process might be regarded as a selective mono-hydroxylation of a CH2-group and shall further be elaborated into a broadly applicable process with a special focus on the development of an enantioselective version. Moreover, the in-situ generated ketones could react in analogy to the hydrogen-autotransfer catalysis with amines, C-H-acidic carbonyl groups or aldehydes to the corresponding condensation products which can be reduced using hydrogenation or transferhydrogenation conditions. This one-pot procedure would represent a selective amination or alkylation of a methylene group.