Relay Cross Metathesis for the Iterative Construction of Terpenoids and Synthesis of a Diterpene Benzoate Macrolide of Biogenetic Relevance to the
A Relay Strategy Actuates Pre-Existing Trisubstituted Olefins in Monoterpenoids for Cross-Metathesis with Trisubstituted Alkenes
Mechanistic Studies on the Copper-Catalyzed N-Arylation of Alkylamines Promoted by Organic Soluble Ionic Bases
Synthesis, Characterisation and Reactivity of Copper(I) Amide Complexes and Studies on Their Role in the Modified Ullmann Amination Reaction
Catalytic Asymmetric Bromolactonization Reactions using (DHQD)(2)PHAL-Benzoic Acid Combinations
Dimethylformamide, Dimethylacetamide and Tetramethylguanidine as Nucleophilic Organocatalysts for the Transfer of Electrophilic Bromine
Amidines as Potent Nucleophilic Organocatalysts for the Transfer of Electrophilic Bromine from N-Bromosuccinimide to Alkenes
Planar Chiral PHANOLs as Double Hydrogen Bonding Donor Organocatalysts: Synthesis and Catalysis
Planar Chiral PHANOLs as Organocatalysts for the Diels-Alder Reaction via Double Hydrogen-Bonding to a Carbonyl Group
Improved Synthesis of (+/-)-4,12-Dihydroxy[2.2]paracyclophane and its Enantiomeric Resolution by Enzymatic Methods: Planar Chiral (R)- and (S)-Phanol
As a counterpoint to our natural product work we also developed new organocatalysts for bromination,4,5 including ortho-substituted iodobenzenes.6 This ultimately led to the off-the-shelf use of the Sharpless ligand with carboxylic acid additives for catalytic asymmetric bromolactonisations.7
As a separate area, we have been involved with olefin metathesis chemistry using Grubbs ruthenium based catalysts. In early work, the ability of ruthenium benzylidenes and palladium(0) catalysts to function as orthogonal catalysts was explored.8,9 in 2006, we reported on facile anionic ligand exchange in Hoveyda-Grubs ruthenium benzylidenes,10 and subsequently utilized these observations for a vacuum driven immobilisation of Buchmeister-Hoveyda-Grubbs ruthenium benzylidenes.11 In 2017 we reported that kinetic benchmarking reveals the competence of prenyl groups in ring-closing metathesis.12 In 2020 we reported on the use of a relay strategy to actuate trisubstituted olefins in monoterpenoids for cross-metathesis with trisubstituted alkenes,13 and subsequently utilised this method for the first iterative construction of terpenes using terpenoid building blocks.14
In collaborative work with Dr Rob Davies, we have been been exploring copper catalyzed Ullmann reactions. In 2015, we reported on the synthesis and reactivity of copper(I) amide complexes.15 Subsequently, we have reported mechanistic studies on the copper catalyzed N-arylations of alkyl amines promoted by organic soluble bases,16 mechanistic and performance studies on the ligand-promoted Ullmann amination reaction,17 and new insights into the reaction capabilities of ionic bases in copper-catalysed aminations.18
Olefin metathesis and copper catalyzed methods continue to be active areas of research in the group.
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