Thomas, Stephen

Schneider, Uwe

Greenhalgh, Mark David

Engineering and Physical Sciences Research Council (EPSRC)

2016-11-09T10:10:13Z

2016-11-09T10:10:13Z

2015-11-26

The iron-catalysed hydrofunctionalisation of alkenes and alkynes has been developed to give a range of functionalised products with control of regio-, chemo- and stereochemistry. Using a bench-stable iron(II) pre-catalyst, the hydrosilylation, hydroboration, hydrogermylation and hydromagnesiation of alkenes and alkynes has been achieved. Iron-catalysed hydrosilylation, hydroboration and hydrogermylation of terminal, 1,1- and 1,2-disubstituted alkyl and aryl alkenes and alkynes was developed, in which the active iron catalyst was generated in situ (Scheme A1). Alkyl and vinyl silanes and pinacol boronic esters were synthesised in good to excellent yield in the presence of a range of functional groups. Catalyst loadings as low as 0.07 mol% were demonstrated, along with catalyst turn-over frequencies of up to 60 000 mol h−1. The iron-catalysed formal hydrocarboxylation of a range of styrene derivatives has been developed for the synthesis of α-aryl carboxylic acids using carbon dioxide and ethylmagnesium bromide as the stoichiometric hydride source (Scheme A2). Detailed mechanistic studies have shown this reaction proceeds by iron-catalysed hydromagnesiation to give an intermediate benzylic organomagnesium reagent. The nature of the active catalyst and reaction mechanism have been proposed.

http://hdl.handle.net/1842/17624

en

The University of Edinburgh

Iron-Catalysed, Hydride-Mediated Reductive Cross-Coupling of Vinyl Halides and Grignard Reagents. Le Bailly, B. A. F.; Greenhalgh M. D.; Thomas, S. P. Chem. Commun. 2012, 48, 1580-1582.

Iron-Catalyzed, Highly Regioselective Synthesis of α-Aryl Carboxylic Acids from Styrene Derivatives and CO2. Greenhalgh, M. D.; Thomas, S. P. J. Am. Chem. Soc. 2012, 134, 11900-11903. - Highlighted in Synform, 2012/12: DOI: 10.1055/s-0032-1317501.

Iron-Catalyzed Hydromagnesiation of Olefins. Greenhalgh, M. D.; Thomas, S. P. Synlett 2013, 24, 531-534.

Chemo-, Regio-, and Stereoselective Iron-Catalysed Hydroboration of Alkenes and Alkynes. Greenhalgh, M. D.; Thomas, S. P. Chem. Commun. 2013, 49, 11230-11232.

Iron-Catalysed Chemo-, Regio-, and Stereoselective Hydrosilylation of Alkenes and Alkynes Using a Bench-Stable Iron(II) Pre-Catalyst. Greenhalgh, M. D.; Frank D. J.; Thomas, S. P. Adv. Synth. Catal. 2014, 356, 584-590.

Iron-Catalysed Reductive Cross-Coupling of Alkenes. Greenhalgh, M. D.; Thomas, S. P. ChemCatChem 2014, 6, 1520-1522.

Iron-Catalysed Hydromagnesiation: Synthesis and Characterisation of Benzylic Grignard Reagent Intermediate and Application in the Synthesis of Ibuprofen. Greenhalgh, M. D.; Kolodziej, A.; Sinclair F.; Thomas, S. P. Organometallics 2014, 33, 5811-5819.

Broad Scope Hydrofunctionalization of Styrene Derivatives Using Iron-Catalyzed Hydromagnesiation. Jones, A. S.; Paliga, J. F.; Greenhalgh, M. D.; Quibell, J. M.; Steven, A. Thomas, S. P. Org. Lett. 2014, 16, 5964-5967. - Highlighted in Synfacts 2015, 11, 186.

Iron-Catalysed Hydrofunctionalisation of Alkenes and Alkynes. Greenhalgh, M. D.; Jones, A. S.; Thomas, S. P. ChemCatChem 2015, 7, 190-222.

Heterogeneous Catalytic Hydrogenation of C=C and C≡C bonds. Thomas S. P.; Greenhalgh, M. D. in Comprehensive Organic Synthesis, Clayden, J., vol. Ed.; Molander, G. A., Knochel, P., Eds.; Elsevier, 2nd edn., 2014, Vol. 8, pp 564-604.

iron

catalysis

Iron-catalysed hydrofunctionalisation of alkenes and alkynes

Thesis or Dissertation

Doctoral

PhD Doctor of Philosophy