Enolate-directed catalytic C–H functionalization of 2-aryl-1,3-dicarbonyl compounds

Khan, Imtiaz (2015) Enolate-directed catalytic C–H functionalization of 2-aryl-1,3-dicarbonyl compounds. PhD thesis, University of Nottingham.

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I) Synthesis of Spiroindenes by Enolate-Directed Ruthenium-Catalyzed Oxidative Annulation of Alkynes with 2-Aryl-1,3-dicarbonyl Compounds

The synthesis of carbocycles by the ruthenium-catalyzed oxidative annulation of alkynes with 2-aryl cyclic 1,3-dicarbonyl substrates is described. Proceeding by the functionalization of C(sp3)–H and C(sp2)–H bonds, and the formation of all-carbon quaternary centers, the reactions provide a diverse range of spiroindenes in good yields and high levels of regioselectivity.

II) Synthesis of Benzopyrans by Pd(II)- or Ru(II)-Catalyzed C–H Alkenylation of 2-Aryl-3-hydroxy-2-cyclohexenones

We have explored the 2-aryl-3-hydroxy-2-cyclohexenones as competent substrates for palladium- and ruthenium-catalyzed C–H alkenylation reactions with terminal alkenes. This process affords benzopyrans, in most cases, with good functional group tolerance.

III) Synthesis of Spiroindanes by Palladium-Catalyzed Oxidative Annulations of 1,3-Dienes Involving C–H Functionalization

1,3-Dienes have been an underexplored class of substrates in catalytic oxidative annulation reactions involving C‒H functionalization. The synthesis of spiroindanes by the palladium-catalyzed oxidative annulation of 1,3-dienes with 2-aryl cyclic 1,3-dicarbonyl compounds is described. Several examples of the dearomatizing oxidative annulation of 1,3-dienes with 1-aryl-2-naphthols are also presented.

IV) Enantioselective Spiroindene Formation via C‒H Functionalization Using Chiral Cyclopentadienyl Rhodium Catalysts

A chiral cyclopentadienyl rhodium ligand with an atropchiral biaryl backbone enables an asymmetric synthesis of spiroindenes from 2-aryl-1,3-dicarbonyl compounds and alkynes. The process affords a range of products with all-carbon quaternary center in high yields and excellent enantiselectivities. The good functional group tolerance and broad substrate generality are the advantages of this reaction.

Item Type: Thesis (University of Nottingham only) (PhD)
Supervisors: Lam, H.W.
Woodward, S.
Subjects: Q Science > QD Chemistry > QD450 Physical and theoretical chemistry
Faculties/Schools: UK Campuses > Faculty of Science > School of Chemistry
Item ID: 30261
Depositing User: Khan, Imtiaz
Date Deposited: 17 Mar 2016 15:05
Last Modified: 17 Sep 2016 19:38
URI: http://eprints.nottingham.ac.uk/id/eprint/30261

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