Construction of quaternary stereocentres in the radical-radical cascade cyclisation of barbiturates

Abstract

The development of radical-radical cyclisation cascade triggered by single-electrontransfer to amide-type carbonyl using SmI2-H2O-LiBr is described. This transformationallows the construction of tricyclic scaffolds, diastereoselectively, containing three newstereocentres and one synthetically challenging quaternary centre in a singleoperational step.Barbiturates are ideal templates as alkene radical traps can be attached to carbonand/or nitrogen and cyclisation avoids undesired reduction or side product formation.The first electron transfer from SmI2 to form the amide-type radical is reversible, leadingto the possibility of trapping that radical with suitably positioned radical acceptors.

Date of Award	31 Dec 2016
Original language	English
Awarding Institution	The University of Manchester
Supervisor	David Procter (Supervisor) & Daniele Leonori (Supervisor)