Ruthenium-catalysed atom transfer radical addition A radical approach to chloroalkane valorisation

This thesis explores the use of chloroalkanes in ruthenium-catalysed atom transfer radical addition (ATRA), addressing challenges that are understudied in literature and providing new avenues for chlorinated substrates. Chloroalkanes are an abundant class of substrates that are understudied for radical chemistry due to the higher C–Cl bond dissociation energy and overall lower reactivity. Using ruthenium pianostool complexes of the type [Cp*RuCl_x(PR3)_y], the following challenges were studied, supported with mechanistic investigations. Firstly, the use of primary alkyl chlorides, a notoriously difficult class of substrates for ATRA, is explored. Optimising the reaction conditions resulted in improvement of the yields and new insights into the mechanism. Then, using chiral phosphines, the ATRA reaction of CCl4 is performed asymmetrically, resulting in low to moderate enantiomeric excess. Then, a cascade reaction is developed that transforms simple haloalkanes and 2,3-aryl-1,3-butadienes into substituted (dihydro)naphthalenes. Finally, an intermolecular cascade reaction is explored for the one-pot synthesis of chlorinated polymers. Overall, this thesis presents new insights in the use of chloroalkanes for ATRA.