Exploiting Photocatalyzed Reactions Under Continuous Flow Conditions by using Porphyrinoid Systems: (C-FlowPhotoChem)

Abstract

In this project, continuous flow photocatalyzed reactions will be exploited by using porphyrinoid systems as photocatalysts (Figure i). The main objective here is to advance on the promotion and scalability of photocatalyzed process in which already presented some limitations to be performed. In addition, we intend to exploit the huge photocatalytic potential which porphyrins may represent for preparative photocatalyzed reactions (scale-up). Thus, we have selected two relevant reactions which present some technical limitations on the execution in organic synthesis: endoperoxidations/Kornblum-DeLaMare rearrangements and oxidative cyclizations of tertiary amines by using photocatalysis - Double C-H functionalization. In the first part of the project we intend to study the best condition for the endoperoxidation reactions by testing a scope of dienes, all of them under continuous flow generation. Thus, we intend to study the in-line Kornblum-DeLaMare rearrangement aiming at for security, scaling-up of the process as well as the further preparation of phosphorylated inositol and polihydroxylated enzymatic inhibitors. In the second part of this project we intend to evaluate the potential of some porphyrin derivatives for use in SET (single electron transfer) photocatalytic reactions by the generation of tertiary amine radical cations and further reaction with electrophiles aiming at the synthesis of tetrahydroquinoline systems under continuous flow conditions. (AU)