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

在该项目中，一个旨在开发选择性C-H功能化系统的计划，这在一定程度上补充了现有的程序。与现有的方法相反，官能团将不是氧化体系的一部分，而是使用经典的羰基转化来引入。为了发展这一体系，氢自转移催化的基本概念将与连续的钌催化碳氢氧化和还原相结合。最初，阳离子（P^N^N^P）Ru（乙腈）cl -配合物将用于将亚甲基氧化成酮，在加氢或转移加氢条件下，该酮将被相同的催化剂还原。这个过程可以看作是选择性的ch2 -基团的单羟基化，并将进一步阐述为一个广泛适用的过程，并特别关注对映选择性的发展。此外，原位生成的酮类可以与胺、c - h酸性羰基或醛类似于氢自转移催化反应生成相应的缩合产物，这些缩合产物可以在加氢或转移加氢条件下还原。这一锅程序将代表亚甲基的选择性胺化或烷基化。

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.