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  • Journal article
    Bahou K, Braddock DC, Meyer AG, Savage GP, Shi Z, He Tet al., 2019,

    A Relay Strategy Actuates Pre-Existing Trisubstituted Olefins in Monoterpenoids to Form New Trisubstituted Olefins by Cross Metathesis

    <jats:p>&lt;b&gt;&lt;u&gt;Abstract:&lt;/u&gt;&lt;/b&gt; A retrosynthetic disconnection-reconnection analysis of epoxypolyenes – substrates that can undergo cyclization to podocarpane-type tricycles – reveals relay-actuated Δ&lt;sup&gt;6,7&lt;/sup&gt;-functionalized monoterpenoid alcohols for ruthenium benzylidene catalyzed olefin cross metathesis with homoprenyl benzenes. Successful implementation of this approach provided several epoxypolyenes as expected (&lt;i&gt;E&lt;/i&gt;:&lt;i&gt;Z&lt;/i&gt;, ca. 2-3:1). The method is further generalized for the cross metathesis of pre-existing trisubstituted olefins in other relay-actuated Δ&lt;sup&gt;6,7&lt;/sup&gt;-functionalized monoterpenoid alcohols with various other trisubstituted alkenes to form new trisubstituted olefins. Epoxypolyene cyclization of an enantiomerically pure, but geometrically impure, epoxypolyene substrate provides an enantiomerically pure, trans-fused, podocarpane-type tricycle (from the &lt;i&gt;E&lt;/i&gt;-geometrical isomer).&lt;br&gt;</jats:p>
  • Journal article
    Bahou K, Braddock DC, Meyer AG, Savage GP, Shi Zet al., 2019,

    Relay Cross Metathesis for the Iterative Ascent of the Terpenoids

    <jats:p>We report the design and implementation of a relay crossmetathesis (ReXM) reaction for the ascent of the terpenoids in an iterative protocol. The method features the reaction of naturally occurring terpenoid building blocks – with preexisting trisubstituted olefins – which combine to construct a new trisubstituted olefin resulting in a five-carbon unit homologation. Subsequent functional group manipulation allows for the method to be repeated in aniterative fashion. The method is used for the synthesis of a diterpenebenzoate macrolide of biogenetic relevance to the bromophycolide family of natural products.</jats:p>
  • Journal article
    Bahou K, Braddock DC, Meyer AG, Savage GP, Shi Zet al., 2019,

    Relay Cross Metathesis for the Ascent of the Terpenoids

    <jats:p>We report the design and implementation of a relay cross metathesis (ReXM) reaction for the ascent of the terpenoids in an iterative protocol using naturally occurring terpenoid building blocks. The method is used for the synthesis of a diterpene-benzoate macrolide of biogenetic relevance to the bromophycolide family of natural products.</jats:p>
  • Journal article
    Lo Q, Sale D, Braddock D, Davies Ret al., 2019,

    New insights into the reaction capabilities of ionic organic bases in cu-catalysed amination

    , European Journal of Organic Chemistry, Vol: 2019, Pages: 1944-1951, ISSN: 1099-0690

    The application of ionic organic bases in the copper‐catalyzed amination reaction (Ullmann reaction) has been studied at room temperature, with sub‐mol‐% catalyst loadings, and with more challenging amines at elevated temperatures. The cation present in the base has been shown to have little effect on the reaction at standard catalyst and ancillary ligand loadings, whereas the choice of anion is crucial for good reactivity. A substrate scope carried out at room temperature with the best performing bases, TBAM and TBPM, showed both bases to be highly effective under these mild reaction conditions. Moreover, under sub‐mol % catalyst loadings and room temperature conditions, TBPM gave good to excellent yields for a number of different amines and functionalized aryl iodides (14 examples). However, reactions involving more challenging amines gave little or no yield. By using more forceful conditions (120 °C) moderate to excellent yields of cross‐coupled products containing more challenging amines was achievable using TBPM and to a lesser extent with TBAM. As part of this work a study on the stability of the organic bases at 120 °C was undertaken. TBAM is shown to decompose to give nBu3N and mono‐butylmalonate at higher temperatures, and this can be correlated to a decrease in performance in the coupling reaction. The phosphonium cations in TBPM did not undergo analogous reactivity but were shown instead to experience some degree of deprotonation at the α‐CH2 to generate phosphonium ylides. This however did not lead to a significantly degradation in the activity of the TBPM in the cross‐coupling reaction.
  • Journal article
    Braddock DC, Lickiss PD, Rowley BC, Pugh D, Purnomo T, Santhakumar G, Fussell SJet al., 2018,

    Tetramethyl Orthosilicate (TMOS) as a Reagent for Direct Amidation of Carboxylic Acids

    , ORGANIC LETTERS, Vol: 20, Pages: 950-953, ISSN: 1523-7060
  • Journal article
    Lo QA, Sale D, Braddock DC, Davies RPet al., 2018,

    Mechanistic and Performance Studies on the Ligand-Promoted Ullmann Amination Reaction

    , ACS CATALYSIS, Vol: 8, Pages: 101-109, ISSN: 2155-5435
  • Journal article
    Bahou KA, Braddock DC, Meyer AG, Savage GPet al., 2017,

    Kinetic Benchmarking Reveals the Competence of Prenyl Groups in Ring-Closing Metathesis

    , ORGANIC LETTERS, Vol: 19, Pages: 5332-5335, ISSN: 1523-7060
  • Journal article
    Clarke J, Bonney KJ, Yaqoob M, Solanki S, Rzepa HS, White AJP, Millan DS, Braddock DCet al., 2016,

    Epimeric Face-Selective Oxidations and Diastereodivergent Transannular Oxonium Ion Formation Fragmentations: Computational Modeling and Total Syntheses of 12-Epoxyobtusallene IV, 12-Epoxyobtusallene II, Obtusallene X, Marilzabicycloallene C, and Marilzabicycloallene D

    , Journal of Organic Chemistry, Vol: 81, Pages: 9539-9552, ISSN: 0022-3263

    The total syntheses of 12-epoxyobtusallene IV, 12-epoxyobtusallene II, obtusallene X, marilzabicycloallene C, and marilzabicycloallene D as halogenated C15-acetogenin 12-membered bicyclic and tricyclic ether bromoallene-containing marine metabolites from Laurencia species are described. Two enantiomerically pure C4-epimeric dioxabicyclo[8.2.1]tridecenes were synthesized by E-selective ring-closing metathesis where their absolute stereochemistry was previously set via catalytic asymmetric homoallylic epoxidation and elaborated via regioselective epoxide-ring opening and diastereoselective bromoetherification. Epimeric face-selective oxidation of their Δ12,13 olefins followed by bromoallene installation allowed access to the oppositely configured 12,13-epoxides of 12-epoxyobtusallene II and 12-epoxyobtusallene IV. Subsequent exploration of their putative biomimetic oxonium ion formation-fragmentations reactions revealed diastereodivergent pathways giving marilzabicycloallene C and obtusallene X, respectively. The original configurations of the substrates evidently control oxonium ion formation and their subsequent preferred mode of fragmentation by nucleophilic attack at C9 or C12. Quantum modeling of this stereoselectivity at the ωB97X-D/Def2-TZVPPD/SCRF = methanol level revealed that in addition to direction resulting from hydrogen bonding, the dipole moment of the ion-pair transition state is an important factor. Marilzabicycloallene D as a pentahalogenated 12-membered bicyclic ether bromoallene was synthesized by a face-selective chloronium ion initiated oxonium ion formation-fragmentation process followed by subsequent bromoallene installation.
  • Journal article
    Braddock DC, Mahtey A, Rzepa HS, White AJPet al., 2016,

    Stable bromoallene oxides

    , Chemical Communications, Vol: 52, Pages: 11219-11222, ISSN: 1364-548X

    The first stable bromoallene oxides were obtained by the DMDO epoxidation of 1-bromo-1,3-di-tert-alkylallenes, producing the first crystalline allene oxide of any kind. The epoxidations are regioselective for the bromine-bearing Δ1,2 alkene, and also face selective producing single diastereomer E-olefin products.
  • Journal article
    Sung S, Sale D, Braddock DC, Armstrong A, Brennan C, Davies RPet al., 2016,

    Mechanistic Studies on the Copper-Catalyzed N-Arylation of Alkylamines Promoted by Organic Soluble Ionic Bases

    , ACS CATALYSIS, Vol: 6, Pages: 3965-3974, ISSN: 2155-5435
  • Journal article
    Campbell J, Burgal JDS, Szekely G, Davies RP, Braddock DC, Livingston Aet al., 2016,

    Hybrid polymer/MOF membranes for Organic Solvent Nanofiltration (OSN): Chemical modification and the quest for perfection

    , Journal of Membrane Science, Vol: 503, Pages: 166-176, ISSN: 0376-7388

    One of the main challenges in the field of Organic Solvent Nanofiltration (OSN) is to improve the selectivity of membranes, allowing the separation of closely related solutes. This objective might be achieved by constructing membranes with uniform porous structures. Hybrid Polymer/Metal Organic Framework (MOF) membranes were prepared by in-situ growth (ISG) of HKUST-1 within the pores of polyimide membranes. To improve the performances of ISG membranes, chemical modification was performed. Aryl carboxylic acid moieties were introduced to polyimide P84 ultrafiltration membranes allowing coordination of the HKUST-1 directly on to the polymer. Chemically modified ISG membranes outperformed non-modified ISG membranes in both solute retentions and permeance. Retentions of polystyrene solute in acetone were used to calculate theoretical pore size distributions for each of the membranes tested. It was found that the chemically modified ISG membrane had he narrowest calculated pore size distribution.
  • Journal article
    Sung S, Braddock DC, Armstrong A, Brennan C, Sale D, White AJP, Davies RPet al., 2015,

    Synthesis, Characterisation and Reactivity of Copper(I) Amide Complexes and Studies on Their Role in the Modified Ullmann Amination Reaction

    , CHEMISTRY-A EUROPEAN JOURNAL, Vol: 21, Pages: 7179-7192, ISSN: 0947-6539
  • Journal article
    Campbell J, Davies RP, Braddock DC, Livingston AGet al., 2015,

    Improving the permeance of hybrid polymer/metal-organic framework (MOF) membranes for organic solvent nanofiltration (OSN) - development of MOF thin films via interfacial synthesis

    , JOURNAL OF MATERIALS CHEMISTRY A, Vol: 3, Pages: 9668-9674, ISSN: 2050-7488
  • Journal article
    Campbell J, Szekely G, Davies RP, Braddock DC, Livingston AGet al., 2014,

    Fabrication of hybrid polymer/metal organic framework membranes: mixed matrix membranes versus in situ growth

    , Journal of Materials Chemistry A, Vol: 2, Pages: 9260-9271, ISSN: 2050-7488

    Hybrid polymer/metal organic framework (MOF) membranes have been prepared using either a mixed matrix membrane (MMM) or in situ growth (ISG) approach and were evaluated for application in organic solvent nanofiltration (OSN). MMMs were produced by dispersing pre-formed particles of the MOF HKUST-1 in polyimide P84 dope solutions. MMMs demonstrated both (i) higher rejections of styrene oligomers and (ii) lower flux decline than the polymeric control membranes. Furthermore, an alternative hybrid membrane fabrication methodology – in situ growth (ISG) of HKUST-1 in integrally skinned asymmetric polymer membrane supports – has been successfully demonstrated. Ultrafiltration support membranes were submerged in HKUST-1 precursor solutions in order to promote the growth of MOF within the porous structure of the polymer membranes. The presence of HKUST-1 in the membranes was proven with X-ray powder diffraction (XRPD). Energy-dispersive X-ray spectroscopy (EDX) was used to reveal the distribution of HKUST-1 throughout the ISG membranes, and was found to be even across the surface and throughout the cross-section. The ISG membranes also had higher solute rejections and lower flux decline than the MMMs.
  • Journal article
    Braddock DC, Sbircea D-T, 2014,

    Proof-of-principle direct double cyclisation of a linear C<sub>15</sub>-precursor to a dibrominated bicyclic medium-ring ether relevant to <i>Laurencia</i> species

    , CHEMICAL COMMUNICATIONS, Vol: 50, Pages: 12691-12693, ISSN: 1359-7345

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