Yr Athro Rebecca Melen

Lecturer in Inorganic Chemistry

Links

Research Interests

Main Group chemistry has undergone a renaissance in recent years with the realisation that the reactivity of main group elements often closely resembles that of transition metals, with recent studies revealing that main group elements can act as homogenous catalysts for a range of transformations. The development of main group alternatives to conventional transition metal catalysts is an emerging $acirc; hot topic$acirc; . Previous research by Melen pioneered the use of Main-Group complexes in the catalytic dehydrocoupling of amino-boranes [1] for which she received the RSC Dalton Young Researcher Award (2013). Her subsequent studies on heterocyclic synthesis via Main Group Lewis acid promoted organic transformations [2] coupled with her dehydrocoupling studies led to her European Young Researcher Award (2014). Amongst her published research, she has several articles designated as $acirc; hot papers$acirc; and/or reflected in Front/Inside Cover artwork. Research projects in the Melen group draw together several different areas of chemistry including organic and inorganic synthesis, main group chemistry, catalysis and implement a range of physical characterisation methods (including multinuclear NMR and X-ray diffraction) supported by computational studies.

References:

[1] Chem. Commun., 2011, 47, 2682; Chem. Sci., 2011, 2, 155; RSC Advances, 2012, 2, 2191.

[2] Chem. Eur. J., 2013, 19, 11928; J. Am. Chem. Soc., 2014, 136, 777; Chem. Commun., 2014, 50, 1161 (inside cover); Chemical Commun., 2014, 50, 7243-7245 (Front cover).

Date
Type

2024

Boruah, T., Ishizeki, R., Roldan, A., Melen, R. L. and Wirth, T. 2024. Flow electrosynthesis of phosphinamides and phosphoramidates through P–N coupling †. Green Chemistry (10.1039/d4gc04450a)
Yu, C., Leitch, J. A., Gierlichs, L., Das, S., Porch, A., Melen, R. L. and Browne, D. L. 2024. Use of microwave dielectric spectroscopy for the In Actu assessment of frustrated Lewis Pair encounter complexes. Journal of the American Chemical Society 146(29), pp. 19809–19817. (10.1021/jacs.4c02736)
Pramanik, M., Das, S., Babaahmadi, R., Pahar, S., Wirth, T., Richards, E. and Melen, R. L. 2024. B(C6F5)3-catalyzed selective C-H chalcogenation of arenes and heteroarenes. Chem (10.1016/j.chempr.2024.05.025)
Pahar, S., van Ingen, Y., Babaahmadi, R., Kariuki, B. M., Wirth, T., Richards, E. and Melen, R. L. 2024. Diverse reactivity of amidinate-supported boron centers with the hypersilyl anion and access to a monomeric secondary boron hydride. Inorganic Chemistry 63(18), pp. 8302–8311. (10.1021/acs.inorgchem.4c00612)
Alotaibi, N. et al. 2024. B(C6F5)3-catalysed alkylation of imidazo[1,2-a]pyridines using α,β-unsaturated ketones. European Journal of Organic Chemistry 27(12), article number: e202400022. (10.1002/ejoc.202400022)
Elsherbeni, S. A., Melen, R. L., Pulis, A. P. and Morrill, L. C. 2024. Accessing highly substituted indoles via B(C6F5)3-catalyzed secondary Alkyl Group Transfer. The Journal of Organic Chemistry 89(6), pp. 4244-4248. (10.1021/acs.joc.4c00025)
Guerzoni, M. G., van Ingen, Y., Babaahmadi, R., Wirth, T., Richards, E. and Melen, R. L. 2024. An un-forgotten classic: the nitro-Mannich reaction between nitrones and silyl nitronates catalysed by B(C6F5)3 †. Chemical Science 15(7) (10.1039/d3sc05672d)

2023

Khan, M. N., van Ingen, Y., Boruah, T., McLauchlan, A., Wirth, T. and Melen, R. L. 2023. Advances in CO2 activation by frustrated Lewis pairs: from stoichiometric to catalytic reactions. Chemical Science 14(47), pp. 13661-13695. (10.1039/d3sc03907b)
Pahar, S., Górecka, A., Richards, E. and Melen, R. L. 2023. Flourishing reactivities of isocyanates and isothiocyanates using group 13 elements. Cell Reports Physical Science 4(12), article number: 101745. (10.1016/j.xcrp.2023.101745)
Pramanik, M., Guerzoni, M. G., Richards, E. and Melen, R. L. 2023. Recent advances in asymmetric catalysis using p‐block elements. Angewandte Chemie International Edition, article number: e202316461. (10.1002/anie.202316461)
Sokolnicki, T. et al. 2023. Reactivity of a series of triaryl borates, B(OAr x) 3, in hydroboration catalysis. Dalton Transactions 52(44), pp. 16118-16122. (10.1039/d3dt03333c)
Pulis, A. P., Morrill, L. C., Melen, R. L., Gillions, J. P., Elsherbeni, S. A., Winfrey, L. and Yun, L. 2023. Recent advances in catalysis using organoborane-mediated hydride abstraction. Accounts and Rapid Communications in Chemical Synthesis 34 (10.1055/a-2111-9629)
Boruah, T., Melen, R. L. and Wirth, T. 2023. Isodesmic metathesis chemistry: A novel way to recycle P(V). Chem Catalysis 3(8), article number: 100731. (10.1016/j.checat.2023.100731)
Pramanik, M. and Melen, R. L. 2023. Frustrated radical pairs in selective functionalization of inert aliphatic C-H bonds. Chem 9(8), pp. 2060-2062. (10.1016/j.chempr.2023.07.012)
van der Zee, L. J. C., Pahar, S., Richards, E., Melen, R. L. and Slootweg, J. C. 2023. Insights into single-electron-transfer processes in frustrated lewis pair chemistry and related donor-acceptor systems in main group chemistry. Chemical Reviews 123(15), pp. 9653-9675. (10.1021/acs.chemrev.3c00217)
Melen, R. L. and Pramanik, M. 2023. Activation of Diazo Compounds by Fluorinated Triarylborane Catalysts. Synthesis: Journal of Synthetic Organic Chemistry (10.1055/a-2118-3046)
Ali, R., Babaahmadi, R., Didsbury, M., Stephens, R., Melen, R. L. and Wirth, T. 2023. Flow electrochemistry for the N‐Nitrosation of secondary amines. Chemistry - A European Journal 29(32), article number: e202300957. (10.1002/chem.202300957)
Alotaibi, N. et al. 2023. B(3,4,5-F3H2C6)3 Lewis acid-catalysed C3-allylation of indoles. Dalton Transactions 52(16) (10.1039/d3dt00745f)
Richards, E. and Melen, R. L. 2023. Carbenium catalysis toward β-carbolines. Chem Catalysis 3(2), article number: 100511. (10.1016/j.checat.2023.100511)
Alharbi, M., van Ingen, Y., Roldan Martinez, A., Kaehler, T. and Melen, R. 2023. Synthesis and Lewis acidity of fluorinated triaryl borates. Dalton Transactions 52(6), pp. 1820-1825. (10.1039/D2DT04095F)
Pramanik, M. and Melen, R. L. 2023. Metal-free routes from carbon monoxide to ketenes. Chem 9(2) (10.1016/j.chempr.2023.01.014)
Stefkova, K., Guerzoni, M. G., van Ingen, Y., Richards, E. and Melen, R. L. 2023. B(c6f5)3-catalyzed diastereoselective and divergent reactions of vinyldiazo esters with nitrones: synthesis of highly functionalized diazo compounds. Organic Letters 25(3), pp. 500-505. (10.1021/acs.orglett.2c04198)

2022

Kustiana, B. A., Melen, R. L. and Morrill, L. C. 2022. One-pot synthesis of styrene derivatives from allyl silanes via b(c6f5)3-catalyzed isomerization-Hiyama coupling. Organic Letters 24(47), pp. 8694-8697. (10.1021/acs.orglett.2c03584)
Guerzoni, M. G., Dasgupta, A., Richards, E. and Melen, R. L. 2022. Enantioselective applications of frustrated Lewis pairs in organic synthesis. Chem Catalysis 2(11), pp. 2865-2875. (10.1016/j.checat.2022.09.007)
Dasgupta, A. et al. 2022. Chemo- and regio-selective amidation of indoles with isocyanates using borane Lewis acids. Catalysis Science & Technology 12(19), pp. 5982-5990. (10.1039/D2CY01441F)
Inoue, S., Melen, R. L. and Harder, S. 2022. Main Group Catalysis. European Journal of Inorganic Chemistry 2022(26), pp. e202200414. (10.1002/ejic.202200414)
Kustiana, B. A., Elsherbeni, S. A., Linford‐Wood, T. G., Melen, R. L., Grayson, M. N. and Morrill, L. C. 2022. B(C 6 F 5 ) 3 ‐Catalyzed E ‐selective isomerization of alkenes. Chemistry - A European Journal, article number: e202202454. (10.1002/chem.202202454)
Dasgupta, A. et al. 2022. Lewis acid assisted Brønsted acid catalysed decarbonylation of Isocyanates: a combined DFT and experimental study. Chemistry - A European Journal 28(45), article number: e202201422. (10.1002/chem.202201422)
Kuveke, R. E. H. et al. 2022. An international study evaluating elemental analysis. ACS Central Science 8(7), pp. 855-863. (10.1021/acscentsci.2c00325)
Kaehler, T. et al. 2022. Borane promoted aryl transfer reaction for the synthesis of α-aryl functionalised β-hydroxy and β-keto esters. Organic and Biomolecular Chemistry 20(21), pp. 4298-4302. (10.1039/D2OB00643J)
Guerzoni, M. G., van Ingen, Y. and Melen, R. L. 2022. Recent applications of fluorinated arylborane derivatives. In: Perez, P. J. ed. Advances in Organometallic Chemistry., Vol. 78. Academic Press, pp. 133-187., (10.1016/bs.adomc.2022.03.004)
Babaahmadi, R., Dasgupta, A., Hyland, C. J. T., Yates, B. F., Melen, R. L. and Ariafard, A. 2022. Understanding the influence of donor-acceptor diazo compounds on the catalyst efficiency of B(C6F5)3 towards carbene formation. Chemistry - A European Journal 28(11), article number: e202104376. (10.1002/chem.202104376)
Dasgupta, A., Pahar, S., Babaahmadi, R., Gierlichs, L., Yates, B. F., Ariafard, A. and Melen, R. L. 2022. Borane catalyzed selective diazo cross-coupling towards pyrazoles. Advanced Synthesis & Catalysis 364(4), pp. 773-780. (10.1002/adsc.202101312)
Walkowiak, J., Szyling, J., Franczyk, A. and Melen, R. 2022. Hydroelementation of diynes. Chemical Society Reviews 51(3), pp. 869-994. (10.1039/d1cs00485a)
Dasgupta, A., Richards, E. and Melen, R. L. 2022. Triarylborane catalyzed carbene transfer reactions using diazo precursors. ACS Catalysis 12, pp. 442-452. (10.1021/acscatal.1c04746)

2021

Dasgupta, A. and Melen, R. L. 2021. Shared success - s-block cooperativity toward triazoles. Chem Catalysis 1(6), pp. 1158-1160. (10.1016/j.checat.2021.10.020)
Dasgupta, A. et al. 2021. Tris(pentafluorophenyl)borane-catalyzed carbenium ion generation and autocatalytic pyrazole synthesis-a computational and experimental study. Angewandte Chemie International Edition 60(46), pp. 24395-24399. (10.1002/anie.202109744)
Dasgupta, A. et al. 2021. Tris(pentafluorphenyl)boran-katalysierte Erzeugung von Carbenium-Ionen und autokatalytische Pyrazol-Synthese – eine theoretische und experimentelle Studie. Angewandte Chemie 133(46), pp. 24599-24604. (10.1002/ange.202109744)
Kaehler, T. and Melen, R. L. 2021. Comparative study of fluorinated triarylalanes and their borane counterparts. Cell Reports Physical Science 2(10), article number: 100595. (10.1016/j.xcrp.2021.100595)
Heard, M. J., Stefkova, K., van Ingen, Y. and Melen, R. L. 2021. Frustrated Lewis pairs in organic synthesis. In: Reference Module in Chemistry, Molecular Sciences and Chemical Engineering. Elsevier, (10.1016/B978-0-12-820206-7.00041-X)
Stefkova, K., Heard, M. J., Dasgupta, A. and Melen, R. L. 2021. Borane catalysed cyclopropenation of arylacetylenes. Chemical Communications 57(55), pp. 6736-6739. (10.1039/D1CC01856F)
Stefkova, K., Carden, J. L. and Melen, R. L. 2021. Frustrated Lewis pairs in catalysis. In: Chemistry, Molecular Sciences and Chemical Engineering. Elsevier Reference Collection Elsevier, (10.1016/B978-0-12-823144-9.00011-X)
Gazis, T. A., Carden, J. L., Alharbi, M. M. and Melen, R. L. 2021. Triarylboranes in the activation of azo-containing compounds. In: Encyclopedia of Inorganic and Bioinorganic Chemistry. Wiley, (10.1002/9781119951438.eibc2780)
Dasgupta, A., Thiehoff, C., Newman, P. D., Wirth, T. and Melen, R. L. 2021. Reactions promoted by hypervalent iodine reagents and boron Lewis acids. Organic and Biomolecular Chemistry 19(22), pp. 4852-4865. (10.1039/D1OB00740H)
Dasgupta, A. et al. 2021. Site-selective Csp3–Csp/Csp3–Csp2 cross-coupling reactions using frustrated Lewis pairs. Journal of the American Chemical Society 143(11), pp. 4451-4464. (10.1021/jacs.1c01622)
Basak, S., Winfrey, L., Kustiana, B. A., Melen, R. L., Morrill, L. C. and Pulis, A. P. 2021. Electron deficient borane-mediated hydride abstraction in amines: stoichiometric and catalytic processes. Chemical Society Reviews 50(6), pp. 3721-3737. (10.1039/D0CS00531B)
Ayan, D., Richards, E. and Melen, R. 2021. Frustrated radical pairs: insights from EPR spectroscopy. Angewandte Chemie International Edition 60(1), pp. 53-65. (10.1002/anie.202010633)

2020

Gazis, T. A., Willcox, D. and Melen, R. L. 2020. Lewis acidic boranes in frustrated Lewis pair chemistry. In: Frustrated Lewis Pairs., Vol. 2. Molecular Catalysis, pp. 209-235., (10.1007/978-3-030-58888-5_6)
Nori, V., Dasgupta, A., Babaahmadi, R., Carlone, A., Ariafard, A. and Melen, R. 2020. Triarylborane catalysed n-alkylation of amines with aryl esters. Catalysis Science and Technology 10, pp. 7523-7530. (10.1039/D0CY01339K)
Ould, D. M. C., Carden, J. L., Page, R. and Melen, R. L. 2020. Synthesis and reactivity of fluorinated triaryl aluminum complexes. Inorganic Chemistry 59(20), pp. 14891-14898. (10.1021/acs.inorgchem.0c01076)
Dasgupta, A., Babaahmadi, R., Slater, B., Yates, B. F., Ariafard, A. and Melen, R. L. 2020. Borane-ctalyzed stereoselective C–H insertion, cyclopropanation, and ring-opening reactions. Chem 6(9), pp. 2364-2381., article number: VOLUME 6, ISSUE 9, P2364-2381, SEPTEMBER 10, 2020. (10.1016/j.chempr.2020.06.035)
Dasgupta, A., Stefkova, K., Babaahmadi, R., Gierlichs, L., Ariafard, A. and Melen, R. 2020. Triarylborane-catalysed alkenylation reaction of aryl esters with diazo compounds. Angewandte Chemie International Edition 59(36), pp. 15492-15496. (10.1002/anie.202007176)
Dasgupta, A., Stefkova, K., Babaahmadi, R., Gierlichs, L., Ariafard, A. and Melen, R. L. 2020. Triarylboran‐katalysierte Alkenylierungen von Arylestern mit Diazoverbindungen. Angewandte Chemie 132(36), pp. 15621-15626. (10.1002/ange.202007176)
Ould, D. and Melen, R. 2020. Diazaphospholene and diazaarsolene derived homogeneous catalysis. Chemistry - A European Journal 26(44), pp. 9835-9845. (10.1002/chem.202001734)
Sharma, G., Newman, P. D., Melen, R. and Platts, J. A. 2020. Computational design of an intramolecular frustrated Lewis pair catalyst for enantioselective hydrogenation. Journal of Theoretical and Computational Chemistry 19, article number: 2. (10.1142/S0219633620500091)
Basak, S., Alvarez-Montoya, A., Winfrey, L., Melen, R. L., Morrill, L. C. and Pulis, A. P. 2020. B(C6F5)3-catalyzed direct C3 alkylation of indoles and oxindoles. ACS Catalysis 10(8), pp. 4835-4840. (10.1021/acscatal.0c01141)
Stefkova, K., Gierlichs, L., Willcox, D. and Melen, R. L. 2020. Borocations in catalysis. In: Scott, R. A. ed. Encyclopedia of Inorganic and Bioinorganic Chemistry. John Wiley & Sons Ltd., (10.1002/9781119951438.eibc2641)
Carden, J. L., Dasgupta, A. and Melen, R. L. 2020. Halogenated triarylboranes: synthesis, properties and applications in catalysis. Chemical Society Reviews 49(6), pp. 1706-1725. (10.1039/C9CS00769E)
Gazis, T. et al. 2020. 1,3-Carboboration of iodonium ylides. Chemical Communications 56, pp. 3345-3348. (10.1039/C9CC08749D)
Willcox, D., Carden, J. L., Ruddy, A. J., Newman, P. D. and Melen, R. L. 2020. Asymmetric ketone hydroboration catalyzed by alkali metal complexes derived from BINOL ligands. Dalton Transactions 49(8), pp. 2417-2420. (10.1039/D0DT00232A)
Soltani, Y. et al. 2020. Radical reactivity of frustrated Lewis pairs with diaryl esters. Cell Reports Physical Science 1(2) (10.1016/j.xcrp.2020.100016)

2019

Ould, D. M. C., Tran, T. T. P., Rawson, J. M. and Melen, R. L. 2019. Structure-property-reactivity studies on dithiaphospholes. Dalton Transactions 48(45), pp. 16922-16935. (10.1039/C9DT03577J)
Willcox, D. and Melen, R. L. 2019. Borane-catalyzed heterocycle synthesis. Trends in Chemistry 1(6), pp. 625-626. (10.1016/j.trechm.2019.06.011)
Gazis, T. A., Dasgupta, A., Hill, M. S., Rawson, J. M., Wirth, T. and Melen, R. L. 2019. Reactions of hydrazones and hydrazides with Lewis acidic boranes. Dalton Transactions(33), pp. 12391-12395. (10.1039/C9DT01359H)
Willcox, D. and Melen, R. L. 2019. Illuminating Lewis acidity strength. Chem 5(6), pp. 1362-1363. (10.1016/j.chempr.2019.04.001)
Santi, M., Ould, D. M. C., Wenz, J., Soltani, Y., Melen, R. L. and Wirth, T. 2019. Metal-free tandem rearrangement/lactonization: Access to 3,3-disubstituted benzofuran-2-(3H)-ones. Angewandte Chemie International Edition 58(23), pp. 7861-7865. (10.1002/anie.201902985)
Melen, R. L. 2019. Frontiers in molecular p-block chemistry: From structure to reactivity. Science 363(6426), pp. 479-484. (10.1126/science.aau5105)
Zhu, D., LaFortune, J. H. W., Melen, R. L. and Stephan, D. W. 2019. Electrophilic boron carboxylate and phosphinate complexes. Dalton Transactions 48(6), pp. 2038-2045. (10.1039/C8DT04818E)
Carden, J., Gierlichs, L., Wass, D., Browne, D. and Melen, R. 2019. Unlocking the catalytic potential of tris(3,4,5-trifluorophenyl)borane with microwave irradiation. Chemical Communications 55(3), pp. 318-321. (10.1039/C8CC09459D)

2018

Soltani, Y., Adams, S. J., Boerger, J., Wilkins, L. C., Newman, P. D., Pope, S. J. A. and Melen, R. L. 2018. Synthesis and photophysical properties of imine borane adducts towards vapochromic materials. Dalton Transactions 47(36), pp. 12656-12660. (10.1039/C8DT03019G)
Khan, I., Reed-Berendt, B. G., Melen, R. L. and Morrill, L. C. 2018. FLP-catalyzed transfer hydrogenation of silyl enol ethers. Angewandte Chemie International Edition 57(38), pp. 12356-12359. (10.1002/anie.201808800)
Ruddy, A. J., Ould, D. M. C., Newman, P. D. and Melen, R. L. 2018. Push and pull: the potential role of boron in N2 activation. Dalton Transactions 47(31), pp. 10377-10381. (10.1039/C8DT01168K)
Schneider, C., LaFortune, J. H. W., Melen, R. L. and Stephan, D. W. 2018. Lewis and Brønsted basicity of phosphine-diazomethane derivatives. Dalton Transactions 47(36), pp. 12742-12749. (10.1039/C8DT02420K)
Melen, R. and Ould, D. 2018. Arsenic catalysis: Hydroboration of aldehydes using a benzo-fused diaza-benzyloxy-arsole. Chemistry - A European Journal (10.1002/chem.201803508)
Hokamp, T., Mollari, L., Wilkins, L. C., Melen, R. L. and Wirth, T. 2018. Alternative strategies with iodine: fast access to previously inaccessible iodine(III) compounds. Angewandte Chemie International Edition 57(27), pp. 8306-8309. (10.1002/anie.201804642)
Wilkins, L. C., Soltani, Y., Lawson, J. R., Slater, B. and Melen, R. L. 2018. Divergent elementoboration: 1,3-haloboration versus 1,1-carboboration of propargyl esters. Chemistry - A European Journal 24(29), pp. 7364-7368. (10.1002/chem.201801493)
Melen, R. L. 2018. A step closer to metal-free dinitrogen activation: a new chapter in the chemistry of frustrated Lewis pairs. Angewandte Chemie International Edition 57(4), pp. 880-882. (10.1002/anie.201711945)
Melen, R. L. 2018. Metallfreie Stickstoffaktivierung: Ein neues Kapitel in der Chemie frustrierter Lewis-Paare. Angewandte Chemie 130(4), pp. 890-892. (10.1002/ange.201711945)

2017

Melen, R., Soltani, Y. and Wilkins, L. 2017. A comparative assessment of modern cyclization methods of substituted alkynyl esters, ethers, and acids. Synlett 29(1), pp. 01-07. (10.1055/s-0036-1591862)
Wilkins, L. C., Melen, R. L., Platts, J. A. and Newman, P. D. 2017. Amidine functionalized phosphines: tuneable ligands for transition metals. Dalton Transactions 46(41), pp. 14234-14243. (10.1039/C7DT03343E)
Khan, I., Manzotti, M., Tizzard, G. J., Coles, S. J., Melen, R. L. and Morrill, L. C. 2017. Frustrated Lewis pair (FLP)-catalyzed hydrogenation of aza-Morita–Baylis–Hillman adducts and sequential organo-FLP catalysis. ACS Catalysis 7(11), pp. 7748-7752. (10.1021/acscatal.7b03077)
Soltani, Y., Wilkins, L. C. and Melen, R. L. 2017. Stoichiometric and catalytic C-C and C-H bond formation with B(C6F5)3 via cationic intermediates. Angewandte Chemie International Edition 56(39), pp. 11995-11999. (10.1002/anie.201704789)
Wilkins, L. C. and Melen, R. L. 2017. Small molecule activation with frustrated Lewis pairs. In: Encyclopedia of Inorganic and Bioinorganic Chemistry. Wiley, pp. 1-24., (10.1002/9781119951438.eibc2520)
Soltani, Y., Wilkins, L. C. and Melen, R. L. 2017. Stöchiometrische und katalytische C-C- und C-H-Bindungsbildung mit B(C6 F5 )3 über kationische Zwischenstufen. Angewandte Chemie 129(39), pp. 12157-12161. (10.1002/ange.201704789)
Ould, D. M. C. et al. 2017. Investigations into the photophysical and electronic properties of pnictoles and Their pnictenium counterparts. Organometallics 37(5), pp. 712-719. (10.1021/acs.organomet.7b00564)
Tran, T. T. P., Ould, D. M. C., Wilkins, L. C., Wright, D. S., Melen, R. and Rawson, J. M. 2017. Supramolecular aggregation in dithia-arsoles: chlorides, cations and N-centred paddlewheels. Crystengcomm 19(32), pp. 4696-4699. (10.1039/C7CE01117B)
Wilkins, L. C., Santi, N., Luk, L. Y. P. and Melen, R. L. 2017. Reactions of biologically inspired hydride sources with B(C6F5)3. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences 375(2101), article number: 20170009. (10.1098/rsta.2017.0009)
Lawson, J., Wilkins, L. and Melen, R. 2017. Tris(2,4,6-trifluorophenyl)borane: an efficient hydroboration catalyst. Chemistry - a European Journal 23(46), pp. 10997-11000. (10.1002/chem.201703109)
Lawson, J. R. and Melen, R. 2017. Tris(pentafluorophenyl)borane and beyond: modern advances in borylation chemistry. Inorganic Chemistry 56(15), pp. 8627-8643. (10.1021/acs.inorgchem.6b02911)
Wilkins, L. C., Howard, J. L., Burger, S., Frentzel-Beyme, L., Browne, D. L. and Melen, R. L. 2017. Exploring multistep continuous-flow hydrosilylation reactions catalyzed by tris(pentafluorophenyl)borane. Advanced Synthesis and Catalysis 359(15), pp. 2580-2584. (10.1002/adsc.201700349)
Lawson, J. R. and Melen, R. L. 2017. Recent developments and applications of Lewis acidic boron reagents. In: Fairlamb, I. et al. eds. Organometallic Chemistry., Vol. 41. Royal Society of Chemistry, pp. 1-27., (10.1039/9781782626923-00001)
Yin, Q., Soltani, Y., Melen, R. and Oestreich, M. 2017. BArF3-catalyzed imine hydroboration with pinacolborane not requiring the assistance of an additional Lewis base. Organometallics 36(13), pp. 2381-2384. (10.1021/acs.organomet.7b00381)

2016

Melen, R., Less, R. J., Pask, C. M. and Rawson, J. M. 2016. Structural studies of Perfluoroaryldiselenadiazolyl Radicals: Insights into Dithiadiazolyl Chemistry. Inorganic Chemistry 55(22), pp. 11747-11759. (10.1021/acs.inorgchem.6b01771)
Lawson, J., Wilkins, L., Andre, M., Richards, E., Ali, M., Platts, J. A. and Melen, R. 2016. Synthesis and reactivity of N,N’-1,4-diazabutadiene derived borocations. Dalton Transactions 45(41), pp. 16177-16181. (10.1039/C6DT03360A)
Lam, J. et al. 2016. Chiral carbene–borane adducts: precursors for borenium catalysts for asymmetric FLP hydrogenations. Dalton Transactions 45(39), pp. 15303-15316. (10.1039/C6DT02202B)
Wilkins, L. C. and Melen, R. L. 2016. Enantioselective main group catalysis: modern catalysts for organic transformations. Coordination Chemistry Reviews 324, pp. 123-139. (10.1016/j.ccr.2016.07.011)
Wilkins, L. C., Lawson, J. R., Wieneke, P., Rominger, F., Hashmi, A. S. K., Hansmann, M. M. and Melen, R. L. 2016. The propargyl rearrangement to functionalised allyl-boron and borocation compounds. Chemistry - a European Journal 22(41), pp. 14618-14624. (10.1002/chem.201602719)
Wilkins, L. C., Gunther, B. A. R., Walther, M., Lawson, J. R., Wirth, T. and Melen, R. L. 2016. Contrasting frustrated Lewis pair reactivity with selenium- and boron-based Lewis acids. Angewandte Chemie International Edition 55(37), pp. 11292-11295. (10.1002/anie.201605239)
Wilkins, L., Günther, B. A., Walther, M., Lawson, J., Wirth, T. and Melen, R. 2016. Gegensätzliche Reaktivität frustrierter Lewis-Paare mit Selen- und Bor-basierten Lewis-Säuren. Angewandte Chemie 128(37), pp. 11462-11465. (10.1002/ange.201605239)
Melen, R. L. and Stephan, D. W. 2016. Main group transformations. Dalton Transactions 45(14), pp. 5879-5879. (10.1039/C6DT90027E)
Melen, R. L. and Gade, L. H. 2016. New chemistry with anionic NNN pincer ligands. In: Topics in Organometallic Chemistry., Vol. 54. Springer, pp. 179-208., (10.1007/3418_2015_114)

2015

Hansmann, M. M., Melen, R. L., Rudolph, M., Rominger, F., Waderpohl, H., Stephan, D. W. and Hashmi, A. S. K. 2015. Cyclopropanation/carboboration reactions of enynes with B(C6F5)3. Journal of the American Chemical Society 137(49), pp. 15469-15477. (10.1021/jacs.5b09311)
Wilkins, L. et al. 2015. Pathways to functionalized heterocycles: propargyl rearrangement using B(C6F5)3. Organometallics 34(21), pp. 5298-5309. (10.1021/acs.organomet.5b00753)
Wilkins, L., Hamilton, H., Kariuki, B., Hashmi, S., Hansmann, M. and Melen, R. 2015. Lewis acid-base 1,2-addition reactions: synthesis of pyrylium borates from en-ynoate precursors.. Dalton Transactions 45, pp. 5929-5932. (10.1039/C5DT03340C)
Melen, R. L. et al. 2015. Diverging pathways in the activation of allenes with Lewis acids and bases: addition, 1,2-Carboboration, and cyclization. Organometallics 34(16), pp. 4127-4137. (10.1021/acs.organomet.5b00546)
Melen, R. L. 2015. Dehydrocoupling routes to element-element bonds catalysed by main group compounds. Chemical Society Reviews 45, pp. 775-788. (10.1039/c5cs00521c)
Melen, R. L. and Stephan, D. W. 2015. Cycloaddition reactions of (C6F5)2BN3 with dialkyl acetylenedicarboxylates. Dalton Transactions 44(11), pp. 5045-5048. (10.1039/C5DT00316D)
Bähr, A., Wilkins, L., Ollegott, K., Kariuki, B. and Melen, R. L. 2015. σ- versus π-activation of alkynyl benzoates using B(C6F5)3. Molecules 20(3), pp. 4530-4547. (10.3390/molecules20034530)

2014

Deng, Q., Melen, R. L. and Gade, L. H. 2014. Anionic chiral tridentate N-donor pincer ligands in asymmetric catalysis. Accounts of Chemical Research, article number: 140828133938004. (10.1021/ar5002457)
Sauer, D. C., Melen, R. L., Kruck, M. and Gade, L. H. 2014. Chromophores, fluorophores and robust ancillary ligands for molecular catalysts: 1,3-Bis(2-pyridylimino)isoindolines. European Journal of Inorganic Chemistry(28), pp. 4715-N4725. (10.1002/ejic.201402595)
Melen, R. L., Simmonds, H. R., Wadepohl, H., Wood, P. T., Gade, L. H. and Wright, D. S. 2014. Formation of an unusual bis(diguanidinate) ligand via nucleophilic attack of a guanidinate onto a carbodiimide. Australian Journal of Chemistry 67(7), pp. 1030-1036. (10.1071/CH14170)
Hansmann, M. M., Melen, R. L., Rominger, F., Hashmi, A. S. K. and Stephan, D. W. 2014. B(C6F5)3 promoted cyclisation of internal propargyl esters: structural characterisation of 1,3-dioxolium compounds. Chemical Communications 50(55), pp. 7243-7245. (10.1039/c4cc01370k)
Hansmann, M. M., Melen, R. L., Rominger, F., Hashmi, A. S. K. and Stephan, D. W. 2014. Activation of alkynes with B(C6F5)3 – boron allylation reagents derived from propargyl esters. Journal of the American Chemical Society 136(2), pp. 777-782. (10.1021/ja4110842)

2013

Melen, R. L. and Rawson, J. M. 2013. Structural variations on an electron precise theme: Rationalising the structures of main group cages. Coordination Chemistry Reviews 257(7-8), pp. 1232-1243. (10.1016/j.ccr.2012.11.016)
Melen, R. L. 2013. Applications of pentafluorophenyl boron reagents in the synthesis of heterocyclic and aromatic compounds. Chemical Communications 50(10), pp. 1161-1174. (10.1039/c3cc48036d)
Melen, R. L. 2013. Applications and reactivity trends of homoleptic p-block metal amido reagents. Dalton Transactions 42(47), pp. 16449-16465. (10.1039/c3dt52472h)
Melen, R. L., Hansmann, M. M., Lough, A. J., Hashmi, A. S. K. and Stephan, D. W. 2013. Cyclisation versus 1,1-carboboration: reactions of B(C6F5)3 with propargyl amides. Chemistry - a European Journal 19(36), pp. 11928-11938. (10.1002/chem.201301899)
Melen, R. L., Lough, A. J. and Stephan, D. W. 2013. Boron azides in Staudinger oxidations and cycloadditions. Dalton Transactions 42(24), pp. 8674-8683. (10.1039/c3dt50791b)
Melen, R. L. and Stephan, D. W. 2013. Cycloaddition reactions between dicyclohexylboron azide and alkynes. Dalton Transactions 42(14), pp. 4795-4798. (10.1039/c3dt00068k)
Melen, R. L., Eisler, D. J., Hewitt, R. A. and Rawson, J. M. 2013. Synthesis and structural studies on thioimides, R2CNSR and sulfur diimides, R2CNSNCR2. Dalton Transactions 42(11), pp. 3888-3895. (10.1039/c2dt32878j)
Melen, R. L. 2013. Q&A: The bond shifter [interview]. Nature 502(7471), pp. S56-S57. (10.1038/502S56a)

2012

Less, R. J., Melen, R. L. and Wright, D. S. 2012. Catalytic versus stoichiometric dehydrocoupling using main group metals. RSC Advances 2(6), pp. 2191-2199. (10.1039/c2ra00882c)
Melen, R. L., Rawson, J. M. and Eisler, D. J. 2012. Structural studies of copper(II) complexes derived from di-2-pyridyl-ketone, (py)2CO. Polyhedron 47(1), pp. 16-23. (10.1016/j.poly.2012.08.009)
Stokes, F. A. et al. 2012. Structure and Bonding of the Manganese(II) Phosphide Complex (t-BuPH2)(η5-Cp)Mn{μ-(t-BuPH)}2Mn(Cp)(t-BuPH2). Organometallics 31(1), pp. 23-26. (10.1021/om200381p)

2011

Hansmann, M. M., Melen, R. L. and Wright, D. S. 2011. Group 13 BN dehydrocoupling reagents, similar to transition metal catalysts but with unique reactivity. Chemical Science 2(8), pp. 1554-1559. (10.1039/c1sc00154j)
Melen, R. L., McPartlin, M. and Wright, D. S. 2011. An unexpected dependence on the SnII base; reactions of Sn(NR2)2 with aromatic dithiols. Dalton Transactions 40(8), pp. 1649-1651. (10.1039/c0dt01690j)
Cowley, H. J., Holt, M. S., Melen, R. L., Rawson, J. M. and Wright, D. S. 2011. Catalytic dehydrocoupling of Me2NHBH3 with Al(NMe2)3. Chemical Communications 47(9), pp. 2682-2684. (10.1039/c0cc05294a)
Less, R. J., Melen, R. L. and Wright, D. S. 2011. Group 2 (Be-Ba) and Group 12 (Zn-Hg). Organometallic Chemistry : Volume 37 37, pp. 100-114. (10.1039/9781849732802-00100)

2010

McPartlin, M., Melen, R. L., Naseri, V. and Wright, D. S. 2010. Formation and rearrangement of SnII phosphanediide cages. Chemistry - a European Journal 16(29), pp. 8854-8860. (10.1002/chem.201000656)
Chan, W. T., García, F., McPartlin, M., Melen, R. L. and Wright, D. S. 2010. Syntheses and structures of [Me2Si{As(PtBu)3}2] and [(CyP)3SiMe2] (Cy=cyclohexyl, C6H11). Journal of Organometallic Chemistry 695(7), pp. 1069-1073. (10.1016/j.jorganchem.2009.12.011)
Bullock, T. H., Melen, R. L. and Wright, D. S. 2010. Group 2 (Be-Ba) and Group 12 (Zn-Hg). Organometallic Chemistry : Volume 36 36, pp. 168-181. (10.1039/9781847559616-00168)
Clark, E. R., Melen, R. L. and Rawson, J. M. 2010. Oxygen, sulfur, selenium, tellurium and polonium. Annual Reports on the Progress of Chemistry - Section A 106, pp. 119-135. (10.1039/b918371j)

2009

Less, R. J., Melen, R. L., Naseri, V. and Wright, D. S. 2009. Recent perspectives on main group-mediated dehydrocoupling of P–P bonds. Chemical Communications(33), pp. 4929-4937. (10.1039/b907823a)
Haynes, D. A., Melen, R. L. and Rawson, J. M. 2009. Oxygen, sulfur, selenium, tellurium and polonium. Annual Reports on the Progress of Chemistry - Section A 105, pp. 155-164. (10.1039/b818151a)

2008

Bacon, C. E., Eisler, D. J., Melen, R. L. and Rawson, J. M. 2008. Formation of N-bridgehead 1,2,5-thiadiazolium and selenadiazolium rings through an intramolecular cyclisation reaction. Chemical Communications 40, pp. 4924-4926. (10.1039/b809987a)

Research in the Melen group focuses on the use of main group Lewis acids in organic synthesis and catalysis. The research programme includes:

Main group catalyst design including tuning the steric and electronic effects of the Lewis acid.
Applications of main group Lewis acids in organic synthesis and catalytic processes.
Mechanistic studies to determine reaction pathways and the role of the Lewis acid in the reactions using combinations of experimental and theoretical methods.

Recent Progress:

The Lewis acidic nature of Main Group compounds can be tailored electronically and sterically by substituents. We have implemented the Lewis-acid nature of Main Group compounds to drive a range of important chemical transformations which have potential applications in the synthesis of pharmaceutically important organic heterocycles and/or in materials chemistry. Recent results have shown that the boron Lewis acid B(C₆F₅)₃ could promote both stoichiometric (and catalytic) organic cyclisation processes in heterocyclic synthesis (Fig. 1). These studies established that B(C₆F₅)₃ was capable of acting in a similar way to transition metal catalysts allowing the conversion of propargyl amides into oxazoles. Depending on the substituents R and temperature, we were able to identify almost every intermediate in the reaction pathway.

However, the main group Lewis acidic B(C₆F₅)₃ can lead to some very different outcomes than those observed for transition metal catalysed transformations. For example, replacement of the propargyl amide by a propargyl ester leads to marked differences in reactivity. Relating to this, the reactions of B(C₆F₅)₃ with propargyl esters yield allyl boron reagents which can undergo addition to aldehydes to afford novel aldol products in a one-pot reaction (Fig. 2).

CH3102 Sylfeini Cemeg Anorganig

CH3201 Adweithedd a Phriodweddau'r Elfennau a'u Cyfansoddion

CH3402 Ffiniau mewn Dylunio Ligand a Chydlynu Cemeg

CHT401 Datblygiadau Diweddar mewn Cemeg Cydlynu Homogenaidd

Gellir dod o hyd i fanylion modiwlau yn y darganfyddwr cyrsiau.

BA and MSci (1^st Class Honours), University of Cambridge (2004$acirc; 2008); PhD, University of Cambridge (2008-2012, Prof. Dominic Wright); Postdoctoral Fellow, University of Toronto, Canada (2012-2013, Prof. Douglas Stephan); Humboldt Fellow, University of Heidelberg, Germany (2013-2014, Prof. Lutz Gade). Appointed as a Lecturer in Chemistry, Cardiff (2014). Significant awards: RSC Dalton Young Researchers Award (2013); European Young Researchers$acirc; Award (2014).

Contact Details

MelenR@caerdydd.ac.uk
+44 29208 79667

Academyddion yn ennill Gwobrau clodfawr Ymddiriedolaeth Leverhulme

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Sengl neu ddwbl? Deall adweithedd cemegol systemau di-fetel

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Academyddion yn ennill Gwobrau clodfawr Ymddiriedolaeth Leverhulme

Sengl neu ddwbl? Deall adweithedd cemegol systemau di-fetel

Gallai arloesiad cyffrous leihau costau a gwenwyndra prosesau gwneud meddyginiaethau

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