Dimethyl acetylenedicarboxylate

4-Bromophenol (97 %), triphenylphosphine (99 %), tris(dibenzylideneacetone)dipalladium(0) (97 %), extra dry on molecular sieves tetrahydrofuran (THF) (99.5 %), 2,2′-azobis(2-methylpropionitrile) (99 %) (AIBN), extra dry on molecular sieves dichloromethane (DCM) (99.8 %) and ethyl acetate (99 %) were all purchased from Acros Organic (Geel, Belgium). Dimethyl acetylenedicarboxylate 98 %, triphenyl arsine (98 %) and tributyl(vinyl)tin (96 %) were all purchased from Alfa Aesar (Karlsruhe, Germany). Magnesium sulphate (98 %), ethanol (99.5 %), sodium hydroxide and concentrated hydrochloric acid (37 %) were supplied by Carlo Erba (Val de Reuil, France.). Sodium fluoride (99 %), sodium chloride (98 %), methacrylic acid (MMA) (99 %), clomiphene citrate (analytical standard 42 % cis and 58 % trans), 4-hydroxy tamoxifen (>70 %) and EGDMA (98 %) were purchased from Sigma Aldrich (France and UK). Tamoxifen citrate (99 %) was purchased from LKT lab Inc. Acetonitrile (99.9 %) (ACN) was obtained from Fischer Chemicals; acetic acid (99.7 %) and methanol (99.9 %) were all HPLC grade and supplied by Carlo Erba (Val de Reuil, France). AIBN was recrystallised from methanol before use. Clomiphene and tamoxifen were isolated from their corresponding citrate salts using sodium bicarbonate (10 mM) and extracted with DCM. Falcon 96-microplates were purchased from SLS.

Thiophene (≥99%), N-bromosuccinimide (NBS) (99%), N,N-dimethylformamide (DMF) (≥99%), dichloromethane (DCM) (≥99.5%), 2-(tributylstannyl)Thiophene (97%), bis(triphenylphosphine)palladium(II) dichloride [PdCl₂(PPh₃)₂] (98%), N-thionylaniline (PhNSO) (98%), chlorotrimethylsilane [(CH₃)₃SiCl] (≥98%), pyridine (99.8%), xylene (≥99%), triphenylphosphine (Ph₃P) (99%), 3,7-dimethyl-1-octanol (≥98%), potassium phthalimide(98%), hydrazine hydrate (50–60%), octylamine (99%), palladium(II) acetate [Pd(OAc)₂] (98%), anhydrous acetic anhydride (≥99%), acetic acid (≥99%) and tris(o-tolyl)phosphine [P(o-tol)₃] (97%) were purchased from Sigma-Aldrich (Gillingham, UK). Anhydrous tin(II) chloride (98%) and dimethyl acetylenedicarboxylate (98%) were purchased from Alfa Aesar (Heysham, UK). All of the starting materials and reagents obtained from Sigma-Aldrich and Alfa Aesar were utilized without further purification. The majority of the reactions were carried out under argon atmosphere. Anhydrous solvents used for the reactions obtained from Grubbs solvent purification system within the Sheffield University/Chemistry department. 9,10-Bis(4-(dodecyloxy)phenyl)-2,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) anthracene (M3) [21 (link)] was prepared according to literature procedure.