References
In early work we planar chiral (R)- and (S)-PHANOLs1 for their use as to and epoxide groups.2,3
As a counterpoint to our natural product work we also new for bromination,4,5 including .6 This ultimately led to the off-the-shelf use of the Sharpless ligand with carboxylic acid additives for .7 A decade later, kinetic profiling revealed product inhibition in an intermolecular catalytic asymmetric bromesterification of alkenes, which allowed for much reduced catalyst loadings to be used.8 Further kinetic studies demonstrated in a catalytic asymmetric intermolecular bromesterification reaction using a chiral phosphoric acid catalyst.9
As a separate area, we have been involved with olefin metathesis chemistry using Grubbs ruthenium based catalysts. In , the ability of ruthenium benzylidenes and palladium(0) catalysts to function as orthogonal catalysts was .10,11 in 2006, we reported on facile in Hoveyda-Grubs ruthenium benzylidenes,12 and subsequently utilized these observations for a of Buchmeister-Hoveyda-Grubbs ruthenium benzylidenes.13 In 2017 we reported that reveals the competence of prenyl groups in ring-closing metathesis.14 In 2020 we reported on the use of a relay strategy to with trisubstituted alkenes,15 and subsequently utilised this method for the using terpenoid building blocks.16
In collaborative work with Dr Rob Davies, we have been been exploring copper catalyzed Ullmann reactions. In 2015, we reported on the of copper(I) amide complexes.17 Subsequently, we have reported on the copper catalyzed N-arylations of alkyl amines promoted by organic soluble bases,18 on the ligand-promoted Ullmann amination reaction,19 and into the reaction capabilities of ionic bases in copper-catalysed aminations.20
In collaborative work with Dr James Wilton-Ely we are exploring the use of recovered metal pre-catalysts in organic synthesis. In 2021, as part of this effort, we published reviews on 22 and .22 In 2022, we reported on the first use of 23 and in 2024, the use of as catalysts for C-H functionalization and C-N bond formation.24
Following up on our direct amidation methodology using stoichiometric tetramethylorthosilicate ()25 and methyltrimethoxysilane (),26 and having the area in 2021,27 in 2023 we reported as the first silicon-centered molecular catalysts for direct amidation of carboxylic acids with amines.28
Catalyzed methods continue to be active areas of research in the group.
References: [1] Braddock D. C.; MacGilp, I.; Perry, B. G. J. Org. Chem. 2002, 67, 8679-8681. [2] Braddock, D. C.; MacGilp, I. D.; Perry, B. G. Synlett 2003, 1121-1124. [3] Braddock, D. C.; MacGilp, I. D.; Perry, B. G. Adv. Synth. Catal. 2004, 326, 1117-1130. [4] Ahmad, S. M.; Braddock, D. C.; Cansell, G.; Hermitage, S. A. Tetrahedron Lett. 2007, 48, 915-918. [5] Ahmad, S. M.; Braddock, D. C.; Cansell, G.; Hermitage, S. A.; Redmond, J. M.; White, A. J. P. Tetrahedron Lett. 2007, 48, 5948-5952. [6] Braddock, D. C.; Cansell, G. Hermitage, S. A. Chem. Commun. 2006, 2483-2485. [7] Armstrong, A.; Braddock, D. C.; Jones, A. X.; Clark, S. Tetrahedron Lett. 2013, 54, 7004-7008. [8] Braddock D. C.; Lancaster B. M. J.; Tighe, C. J.; White, A. J. P. J. Org. Chem. 2023, 88, 8904–8914. [9] Lancaster, B. M. L; White, A. J. P.; Tighe, C. J.; Braddock, D. C. J. Org. Chem. 2025, 90, 6992–7002. [10] Braddock, D. C.; Wildsmith A. J. Tetrahedron Lett. 2001, 42, 3239-3242. [11] Braddock, D. C.; Matsuno, A. Tetrahedron Lett. 2002, 43, 3305-3308. [12] Tanaka, K.; Bohm, V. P. W.; Chadwick, D.; Roeper, M.; Braddock, D. C. Organometallics 2006, 25, 5696-5698. [13] Braddock, D. C.; Tanaka, K.; Chadwick, D.; Bohm, V. P. W.; Roeper, M. Tetrahedron Lett. 2007, 48, 5301-5303. [14] Bahou, K. A.; Braddock, D. C.; Meyer, A. G.; Savage, G. P. Org. Lett. 2017, 19, 5332–5335. [15] Bahou, K.; Braddock, D. C.; Meyer, A. G.; Savage, G. P.; Shi, Z.; He, T. J. Org. Chem. 2020, 85, 4906-4917. [16] Bahou, K. A.; Braddock, D. C.; Meyer, A. G.; Savage, G. P. Org. Lett. 2020, 22, 3176-3179. [17] Sung, S.; Braddock, D. C.; Armstrong, A.; Brennan, C.; Sale, D.; White, A. J. P.; Davies, R. P. Chem. Eur J. 2015, 21, 7179-7192. [18] Sung, S.; Sale, D.; Braddock, D. C.; Armstrong, A.; Brennan, C.; Davies, R. P. ACS Catal. 2016, 6, 3965–3974. [19] Lo, Q. A.; Sale, D.; Braddock, D. C.; Davies, R. P. ACS Catal. 2018, 8, 101-109. [20] Lo, Q. A.; Sale, D.; Braddock, D. C.; Davies, R. P. Eur. J. Org. Chem. 2019, 1944–1951. [22] McCarthy, S.; Braddock, D. C.; Wilton-Ely, J. D. E. T. Coord. Chem. Rev. 2021, 442, 213925. [22] McCarthy, S.; Lee Wei Jie, A.; Braddock, D.C.; Serpe, A.; Wilton-Ely, J.D.E.T. Molecules 2021, 26, 5217. [23] McCarthy, S.; Desaunay, O.; Lee Wei Jie, A.; Hassatzky, M.; White, A; J. P.; Deplano, P.; Braddock, D. C.; Serpe, A.; Wilton-Ely, J. D. E. T. ACS Sustainable Chem. Eng. 2022, 10, 15726–15734. [24] Jantan, K. A.; Ekart, G.; McCarthy, S.; White, A. J. P.; Braddock, D. C.; Serpe, A.; Wilton-Ely, J. D. E. T. Catalysts, 2024, 14, 295. [25] Braddock, D. C.; Lickiss, P. D.; Rowley, B. C.; Pugh, D.; Purnomo, T.; Santhakumar, G.; Fussell, S. J. Org. Lett. 2018, 20, 950-953. [26] Braddock, D. C.; Davies, J. J.; Lickiss, P. D. Org. Lett. 2022, 24, 1175–1179. [27] Davies, J. J.; Braddock, D. C.; Lickiss, P. D. Org. Biomol. Chem. 2021, 19, 6746-6760. [28] Braddock, D. C.; Rowley, B. C.; Lickiss, P. D.; Fussell, S. J.; Qamar, R.; Pugh, D.; Rzepa, H. S.; White, A. J. P. J. Org. Chem. 2023, 88, 9853–9869.