Chlorodimethylsilane

Allyl chloride, 98% (CAS 107-05-1), tetra-n-butylammonium fluoride (1 M solution in THF, CAS 429-41-4), copper (I) iodide, 98% (CAS 7681-65-4) and N,N-Dimethylformamide, 99.9% (CAS 68-12-2) were obtained from ABCR. Sodium azide (CAS 26628-22-8), diphenylether, 99% (CAS 101-84-8) and triethylamine, 99% (CAS 121-44-8) were obtained from Acros Organics. Karstedt’s catalyst (CAS 11057-89-9), diphenylacetylene, 98% (CAS 501-65-5), chlorodimethylsilane, 98% (CAS 1066-35-9) and lithium aluminum hydride (CAS 16853-85-3) were obtained from Sigma-Aldrich. All chemicals were used as received.
The solvents were purified by distillation under reduced pressure in argon.

Solvents were purified by standard methods before use [25 ]. The 4,4,5,5-tetramethyl-1,3,2-dioxaphospholane 2-oxide was purchased from TCI Chemicals (TCI Europe N. V.- Tokyo Chemical Industry, Brussels, Belgium). All bromoalkenes, 1,8-dibromooctane, bithiophene, and tetrakis(triphenylphosphine)palladium (0) (Pd(PPh₃)₄) were purchased from Fluorochem. n-Butyllithium (1.6 M solution in hexane), Karstedt′s catalyst and chlorodimethylsilane were purchased from Sigma Aldrich (Merck, KGaA, Darmstadt, Germany), and bromotrimethylsilane was purchased from Acros Organics (Thermo Fisher Scientific, Geel, Belgium). All chemicals were used as purchased without further purification. Thin-layer chromatography was performed on Merck TLC plates of silica gel 60, F-254, visualization under UV 254 nm and 365 nm, for column chromatography was used silica gel 60 (Merck).

D3 (98%, Aldrich), DMAP, DMAN, TBD (98%, Aldrich), and TMGN were first dissolved in superdehydrated stabilizer-free THF (99.5%, Wako) and then dried over MS4A for 24 h before use. Chlorodimethylsilane (98%, Aldrich), chlorodimethylvinylsilane (98%, Aldrich), platinum(0)−1,3-divinyltetramethyldisiloxane complex solution (Karstedt’s catalyst) (Pt~2% in xylene, Aldrich) and other reagents were used as received. Industrial-grade PDMS with vinyl end groups and a broad Ð synthesized by equilibrium polymerization, such that the relationship between the branching point and the number of end groups is equivalent to that of 3-armed star-shaped PDMS (VS-7: M_n = 12,000, Lot no. 309001), was generously supplied by Shin-Etsu Chemical Co., Ltd. Benzene-1,3,5-triyltris(dimethylsilanol) (I₃)^{20 (link)} and (thio)ureas^{9 (link)} were synthesized according to previously reported procedures.

Allyl bromide (99%), calcium hydride (CaH₂) (95%), chlorodimethylsilane (98%), N,N-dimethylacrylamide (99%), 4-hydroxybenzophenone (98%), [2-(methacryloyloxy)ethyl]tri-methylammonium chloride solution, 80 wt% in H₂O, Pt on activated charcoal (puriss. 10% Pt), Poly(2-ethyl-2-oxazoline) (PEtOx), sodium persulfate (98%) and triethylamine (99,5%) were purchased from Aldrich (St. Louis, USA). Azobisisobutyronitrile (AiBN) (98%) was obtained from Acros (Geel, Belgium). Potassium carbonate (99%), sodium hydroxide (99%) and sodium sulfate (99%) were purchased from Roth (Karlsruhe, Germany). Diethyl ether (HPLC grade) and toluene (HPLC grade) were obtained from VWR (Radnor, USA) and methanol (HPLC grade) from Fisher Scientific (Waltham, USA). Diethyl ether was dried over sodium and distilled before use. triethylamine was dried over CaH₂ and distilled before use. N,N-dimethylacrylamide was distilled under vacuum before use.