Thiehoff C, Holland M, Daniliuc C, Houk K, Gilmour R. Can acyclic conformational control be achieved via a sulfur-fluorine gauche effect?. Chem Sci. 2015;6:3565-3571 pubmed publisher
..Synergy between experiment and computation has revealed that the gauche effect is only pronounced in structures bearing an electropositive vicinal sulfur atom (S+-O-, SO2). ..
Erdeljac N, Kehr G, Ahlqvist M, Knerr L, Gilmour R. Exploring physicochemical space via a bioisostere of the trifluoromethyl and ethyl groups (BITE): attenuating lipophilicity in fluorinated analogues of Gilenya® for multiple sclerosis. Chem Commun (Camb). 2018;54:12002-12005 pubmed publisher
..This subtle fluorination pattern allows lipophilicity (log D) to be tempered compared to the corresponding CF3 and Et derivatives (CH2CH3 > CH2CF3 > CHFCH2F). ..
Holland M, Metternich J, Daniliuc C, Schweizer W, Gilmour R. Aromatic Interactions in Organocatalyst Design: Augmenting Selectivity Reversal in Iminium Ion Activation. Chemistry. 2015;21:9937 pubmed publisher
..The image depicts how the modes of stereoinduction differ for- N-methylpyrrole to- N-methylindole. Read the full text of the article at 10.1002/chem.201500270. ..
Holland M, Metternich J, Daniliuc C, Schweizer W, Gilmour R. Aromatic Interactions in Organocatalyst Design: Augmenting Selectivity Reversal in Iminium Ion Activation. Chemistry. 2015;21:10031-8 pubmed publisher
..This is absent in the N-methylpyrrole alkylation, thus forming the basis of two competing enantio-induction pathways. A simple L-valine catalyst has been developed that significantly augments this interaction. ..
Holland M, Metternich J, MÃ¼ck Lichtenfeld C, Gilmour R. Cation-Ï€ interactions in iminium ion activation: correlating quadrupole moment & enantioselectivity. Chem Commun (Camb). 2015;51:5322-5 pubmed publisher
..The quadrupole moment of the aryl shielding group is a useful qualitative parameter for predicting selectivity (Qzz < 0 â†’ high es). ..
Santschi N, Wagner S, Daniliuc C, Hermann S, SchÃ¤fers M, Gilmour R. Synthesis of 2-[(18)F]Fluoro-2-deoxyisosorbide 5-mononitrate and Assessment of Its in vivo Biodistribution as Determined by Dynamic Positron Emission Tomography (PET). ChemMedChem. 2015;10:1724-32 pubmed publisher
..Radioisotope labeling of 2F-IS-5MN has, for the first time, allowed observation of the in vivo biodistribution of this organic nitrate by means of dynamic positron emission tomography (PET) in wild-type mice. ..
Aiguabella N, Holland M, Gilmour R. Fluorine-directed 1,2-trans glycosylation of rare sugars. Org Biomol Chem. 2016;14:5534-8 pubmed publisher
..Localised partial charge inversion (C-H(Î´+)â†’ C-F(Î´-)) elicits a reversal of the substrate-based Î±-stereoselectivity, irrespective of the protecting group electronics. ..