One-pot transition metal-catalysed processes for the synthesis of biologically active compounds

QD Chemistry

Mostafa, Mohamed A.B. ; Sutherland, Andrew

University:University of Glasgow

Department:School of Chemistry

关键词: Metal catalysis, one-pot process, Overman rearrangement, ring closing enyne metathesis,halogenation, ionic liquid, N-arylation, C-N coupling, Ullman-type coupling, ionic liquid.;   

Others  :  http://theses.gla.ac.uk/8779/1/2017mostafaphd.pdf

来源: University of Glasgow

【 摘 要 】

The first section of this thesis describes the development of a one-pot Pd(II)-catalysed Overman rearrangement, Ru(II)-catalysed ring closing enyne metathesisreaction and a hydrogen bond-directed Diels-Alder reaction for thediastereoselective synthesis of C-5 substituted aminobicyclo[4.3.0]nonanes ingood yields. To explore the late stage diversification of these compounds, furtherwork investigated a one-pot synthesis of a benzyldimethylsilyl-derived analogue.The synthetic utility of this compound was demonstrated using C–C bond couplingreactions, for the late stage synthesis of a range of sp3-rich bicyclononanescaffolds with up to six stereogenic centres.The second section of this thesis describes the development of a one-pot two-stepprocedure for aryl C–H amination using iron and copper catalysis. Firstly, a mildand highly regioselective method for the bromination (and chlorination) of arenesvia iron(III) triflimide activation of N-bromosuccinimide (or N-chlorosuccinimide)was developed. The scope of both processes was explored for the synthesis of awide range of aromatic compounds and natural products. The one-pot iron(III)-catalysed bromination/Cu(I)-catalysed N-arylation was then studied. Afteroptimisation, the one-pot two-step process allowed the synthesis of a large libraryof para-aminated aryl compounds in high yields as single regioisomers.