Study On The Formation Of Carbon - Oxygen Bond By N - Nitroso - Oriented C - H Bond Activation Under Palladium

In the last decade, Palladium-catalyzed C-H bond functionalization protocols have emerged as a valuable and atom-economical alternative. Due to the effect of directing groups, this kind of reaction could form the C-C bond, C-O bond, C-N bond and C-X bond (X= Cl, Br, I, F) from directed C-H cleavages, which greatly shorten the synthetic steps to the traditional cross-coupling reactions. These reactions have a great researching interest. This paper mainly introduced two kinds of new reactions that could form the C-O bond, which is very important for the organic synthetic reactions.This thesis consists of two parts:1. Palladium-catalyzed direct ortho-Alkoxylation of N-alkyl-N-nitrosoarylaminesA palladium-catalyzed direct ortho-alkoxylation of N-alkyl-N-nitrosoarylamines was developed in which alcohols were used as the alkoxylation reagents and PhI(OAc)2 was employed as the oxidant. The protocol was available for both primary and secondary alcohols. The products were transformed to o-alkoxy-N-alkylanilines expediently by a simple reduction. The reaction exhibited good functional group tolerance. The mild reaction conditions provide a valuable approach to apply this methodology in the synthesis of various compounds.2. Palladium-catalyzed direct ortho-Acyloxylation of N-alkyl-N-nitrosoarylaminesAn efficient and highly regioselective direct ortho-acyloxylation of N-alkyl-N-nitrosoarylamines was developed via the palladium-catalyzed C-H bond activation. This reaction can tolerate a series of functional groups and provide the corresponding acyloxylation products with moderate to good yields. A possible mechanism for the transformation was also proposed.