Novel Methodology Publication Gallery
Early work in the group involved the development of the cyclopropylmethylsilane terminated Prins reaction to give ,1 2 and a silicon-centered for a concise synthesis of lyngbic acid.3 We also reported the first enantiopure chair and twist isomers,4 a of silasultones via dehydrative cyclisation5 and for the for the formation of enantiopure 1,2-diaminodiphenyl ethanes.6,7 Additional efforts in this area resulted in to enantiopure tricyclic amidines.8 As a counterpoint to our natural product work, we also developed for brominations,9 and with the first I(III)-Br bond.10
In 2009, we reported the first generation and trapping of ,11 developed a for asymmetric bromonium ion-induced polyene cyclisations12 and reported an initiated by an enantiomerically pure bromonium ion.13 In related chemistry, we also the stereochemical course of nucleophilic substitution of arylsulphonate based nucleophile assisted leaving groups,14 and the stereospecific dyotropic racemisation of enantiopure D and L 1,2-dibromides.15
In 2018, in collaboration with Professor Paul Lickiss, the use of tetramethylorthosilicate (TMOS) as a reagent for the direct amidation of carboxylic acids.16 This paper was one of the top five 'most read' in Organic Letters for 2018 according to , and also featured in a (Organic Letters Global Enterprise, Erick M. Carreira (Editor-in-Chief), Org. Lett., 2019, 21, 2967–2967) as the most downloaded article from the UK in 2018. In December 2023 it featured as one of '25 Most-Read Organic Letters' in the editorial. In 2021, we published a on the use of stoichiometric silicon reagents for direct amidation,17 and in 2022 we reported on the use of (MTM) as as safer (and, in fact, cheaper) alternative to TMOS for direct amidations.18 In 2023, we reported triarysilanols as the first silicon-centred for direct amidation.19 Further development of direct amidations is a continuing theme in our laboratories.
In 2020 we reported the first methodology for the iterative construction of terpenoids using terpene building blocks with ruthenium benzylidene catalysed relay cross metathesis ('ReXM') reactions as the in the iterations.20
In 2023, in collaboration with Leon Barron from the School of Public Health we on brominated acidic contaminants in drinking water,21 with subsequent of a tribrominated hydroxycyclopentene dione in 2024.22
In 2024, we reported a fortuitous enantiomeric self-rectification in the synthesis of a BINOL derived chiral phosphoric acid, and .23
References: [1] Braddock, D. C.; Badine, D. M.; Gottschalk, T. Synlett 2001, 1909-1912. [2] Braddock, D. C.; Badine, D. M.; Gottschalk, T.; Matsuno, A.; Rodriguez-Lens Synlett 2003, 345-38. [3] Braddock, D. C.; Matsuno, A.; Synlett 2004, 2521-2524.[4] Braddock, D. C.; Cansell, G.; Hermitage, S. A.; White, A. J. P. Tetrahedron: Asymm. 2004, 35, 3123-3129. [5] Braddock, D. C.; Peyralans, J. J.-P. Tetrahedron 2005, 61, 7233-7240. [6] Braddock D. C.; Redmond, J. M.; Hermitage, S. A.; White, A. J. P. Adv. Synth. Catal. 2006, 911-916. [7] Braddock, D. C.; Hermitage, S. A.; Redmond, J. M.; White, A. J. P. Tetrahedron: Asymm. 2006, 17, 2935-2937. [8] Braddock, D. C.; Cailleau, T.; Cansell, G.; Hermitage, S. A.; Pouwer, R. H.; Redmond, J. M.; White, A. J. P. Tetrahedron: Asymm. 2010, 21, 2911-2919. [9] Braddock, D. C.; Cansell, G.; Hermitage, S. A. Synlett 2004, 461-464. [10] Braddock, D. C.; Cansell, G.; Hermitage, S. A.; White A. J. P. Chem. Commun. 2006, 1442-1444. [11] Braddock, D. C.; Hermitage, S. A.; Kwok, L.; Pouwer, R.; Redmond, J. M.; White, A. J. P. Chem. Commun. 2009, 1082-1084. [12] Braddock, D. C.; Marklew, J. S.; Thomas, A. J. F. Chem. Commun. 2011, 47, 9051-9053. [13] Braddock, D. C.; Marklew, J. S.; Foote, K. M.; White. A. J. P. Chirality 2013, 25, 692-700. [14] Braddock, D. C.; Pouwer R. H.; Burton J. W.; Broadwith, P. J. Org. Chem. 2009, 74, 6042-6049. , 7602. [15] Braddock, D. C.; Roy, D.; Lenoir, D.; Moore, E.; Rzepa, H. S.; Wu J. I.-C.; Schleyer, P. v. R. Chem. Commun. 2012, 48, 8943-8945. [16] Braddock, D. C.; Lickiss, P. D.; Rowley, B. C.; Pugh, D.; Purnomo, T.; Santhakumar, G.; Fussell, S. J. Org. Lett. 2018, 20, 950-953. [17] Davies, J. J.; Braddock, D. C.; Lickiss, P. D. Org. Biomol. Chem. 2021, 19, 6746-6760. [18] Braddock, D. C.; Davies, J. J.; Lickiss, P. D. Org. Lett. 2022, 24, 1175–1179. [19] Braddock D. C.; Rowley, B. C.; Lickiss, P. D.; [20] Bahou, K. A.; Braddock, D. C.; Meyer, A. G.; Savage, G. P. Org. Lett. 2020, 22, 3176-3179. [21] Ciccarellia, D.; Braddock, D. C.; Surmand, A. J.; Ivonne Vergara Arenas, B.; Salald, T.; Marczylob, T.; Vineis, P.; Barron, L. P. J. Hazard. Mater. 2023, 448, 130906. [22] Ciccarelli, D.; Lancaster, B. M. J.; Braddock, D. C.; Calvaresi, M.; Mišík, M.; Knasmüller, S.; Mattioli, E. J.; Zerbetto, F.; White, A. J. P.; Marczylo, T.; Gant, T. W.; Barron, L. P. Commun. Chem. 2024, 7, 266. [23] Lancaster, B. M. J.; White, A. J. P.; Braddock, D. C. Chem. Eur. J. 2024, 30, e202403318.