Supporting Information
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- Ἰσμήνη Γερμανού
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1 Supporting Information Straightforward xanthate-mediated synthesis of functional γ-thiolactones and their application to polymer synthesis and modification Marvin Langlais, Ihor Kulai, Olivier Coutelier* and Mathias Destarac* Laboratoire des IMRCP, Université de Toulouse, CNRS UMR 5623, Université Paul Sabatier, 118 route de Narbonne, Toulouse Cedex 9, France Materials... 2 General techniques... 2 Synthesis of diethyl allyphosphonate... 4 Synthesis of xanthate salt XA Synthesis of xanthates XA1 and XA Synthesis of monoadducts M Synthesis of thiolactones TL NMR Spectra General procedures of polymer end-functionalizations Step-growth polymerization S1
2 Materials The following chemicals were used as received; DL-3-methyl-2-butanol (Acros Organics, 98%), carbon disulfide (CS 2, Sigma-Aldrich, > 99%), methyl bromoacetate (Sigma-Aldrich, 98%), methyl 2-bromopropionate (Alfa Aesar, 97%), lauroyl peroxide (LPO, Fluka, > 95%), 1-heptene (Alfa Aesar, 98+%), dimethyl vinylphosphonate (DMVP, Sigma-Aldrich, > 95%), 1H, 1H, 2H-perfluoro-1-hexene (Alfa Aesar, 97%), 1H, 1H, 2H-perfluoro-1-decene (Alfa Aesar, 99%), N-phenylmaleimide (Alfa Aesar, 98+%), diethyl phosphate (Sigma-Aldrich, 98%), allyl bromide (Acros Organics, 99%), tetrabutylammonium bromide (TBAB, Acros Organics, 99+%), silica gel 60 (SiO 2, Sigma-Aldrich, 40-63µm), potassium hydroxide (KOH, VWR, 86,8%) potassium carbonate (K 2 CO 3, Sigma-Aldrich, anhydrous, 99%), sodium sulfate (Na 2 SO 4, anhydrous, Prolabo, 99%), benzyl acrylate (BzA, Alfa Aesar, 97%, stabilized with ca 150 ppm 4-methoxyphenol), methyl acrylate (MA, Sigma-Aldrich, 99%, contains < 100 ppm monomethyl ether hydroquinone as inhibitor), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate (TFOA, Sigma-Aldrich, 97%, contains inhibitor), methoxypoly(ethylene glycol) amine (MPEG-NH 2, Sigma-Aldrich, M n ~ 2000 g.mol -1 ), poly(ethylene glycol) bis(3- aminopropyl) terminated (PEG-diNH 2, Sigma-Aldrich, M n ~ 1500 g.mol -1 ), poly(dimethylsiloxane) bis(3-aminopropyl) terminated (PDMS-diNH 2, Sigma-Aldrich, M n ~ 2500 g.mol -1 ), poly(ethylene glycol) diacrylate (PEG-diacrylate, Sigma-Aldrich, M n ~ 575 g.mol -1 ). The following solvents were used as received; tetrahydrofuran (THF, Sigma-Aldrich, HPLC grade), acetone (Sigma-Aldrich, HPLC grade), dichloromethane (DCM, Sigma-Aldrich, HPLC grade), petroleum ether (Sigma-Aldrich, HPLC grade), ethyl acetate (EtOAc, Sigma- Aldrich, HPLC grade), hexane (Sigma-Aldrich, HPLC grade), toluene (Sigma-Aldrich, HPLC grade). General techniques Nuclear magnetic resonance spectra ( 1 H, 13 C, 31 P and 19 F NMR) were recorded at 298 K on a Bruker Avance 300 MHz instrument. 1 H NMR spectra were recorded at MHz and coupling constants (J) are reported to ± 0.5 Hz. The resonance multiplicities are described as s (singlet), d (doublet), t (triplet), q (quartet) or m (multiplet). 13 C NMR spectra were recorded at MHz, 31 P NMR spectra were recorded at MHz and 19 F NMR spectra were recorded at MHz. Chemical shifts δ are reported in parts per million (ppm) and are S2
3 referenced to the residual solvent peak (CDCl 3 : H = 7.26 ppm and C = ppm; D 2 O: H = 4.79 ppm). IR spectroscopy analyses were carried out using a Thermo Nicolet Nexus spectrometer with Diamond ATR. 16 scans from 600 to 4000 cm -1 were taken and absorptions were reported in wavenumbers (cm -1 ). Size-exclusion chromatography (SEC) analyses were performed on a system composed of an Agilent technologies guard column (PLGel20 µm, mm) and a set of three Waters columns (1 Styragel HR 3, mm and 2 Styragel HR 4, mm). Detection was conducted using a Wyatt Optilab rex refractive index detector. Analyses were performed in THF at 308 K at a flow rate of 1.0 ml/min. Polystyrene (PS) standards ( g.mol -1 ) were used for calibration. High-resolution mass spectroscopy analyses (EI and CI-CH 4 ) were performed using a GCT 1er Waters apparatus. Matrix-assisted laser desorption/ionisation time of flight (MALDI-TOF) analyses were performed on Waters MALDI-TOF Micro MX equipped with a nitrogen laser emitting at λ = 357 nm. All analyses were carried out with 1,8-dihydroxy-9(10H)-anthracenone (Ditrhanol) as matrix and NaI salt as cationic agent. S3
4 Synthesis of diethyl allyphosphonate Diethyl allylphosphonate DEAP C 7 H 15 O 3 P M = g.mol -1 Diethylphosphite (13.81 g, 0.1 mol), allyl bromide (15 g, 0.12 mol), K 2 CO 3 (21 g, 0.15 mol) and TBAB (1.61 g, 5 mmol) were refluxed in THF (200 ml) during 24 h. Then the reaction mixture was concentred under reduced pressure, solubilised in deionized water (400 ml) and extracted with DCM (3 100 ml). The organic phase was dried over anhydrous Na 2 SO 4 and concentrated under reduced pressure. The oil was distillated under vacuum to yielded DEAP as a colorless liquid (16.1 g, 90%). 1 H NMR ( MHz, CDCl 3, 298K) δ = (m, 1H, CH 2 =CHCH 2 P), (m, 2H, CH 2 =CHCH 2 P), (m, 4H, O=P(CH 2 CH 3 ) 2 ), (m, 2H, CH 2 =CHCH 2 P), (t, J = 7.1 Hz, 6H, O=P(CH 2 CH 3 ) 2 ). 13 C{ 1 H} NMR (75.47 MHz, CDCl 3, 298K) δ = (CH 2 =CHCH 2 P), (CH 2 =CHCH 2 P), (O=P(OCH 2 CH 3 ) 2 ), (CH 2 =CHCH 2 P), (O=P(OCH 2 CH 3 ) 2 ). 31 P{ 1 H} NMR ( MHz, CDCl 3, 298K) δ = Synthesis of xanthate salt XA0 Potassium O-(3-methylbutan-2-yl) carbonodithioate XA0 C 6 H 11 KOS 2 M = g.mol -1 3-methylbutan-2-ol (101 g, 1.13 mol), KOH (63.65 g, 1.13 mol) and CS 2 (90.7 g, 1.19 mol) were stirred in THF (500 ml) at room temperature until total dissolution of KOH. Then, the solution was concentrated under reduced pressure, triturated with pentane and filtered on Büchner. The compound XA0 was obtained as a yellow solid (185 g, 80%). S4
5 1 H NMR ( MHz, D 2 O, 298K) δ = 5.31 (p, J = 6.4 Hz, 1H, (CH 3 ) 2 CHCH(O)CH 3 ), (m, 1H, (CH 3 ) 2 CHCH(O)CH 3 ), 1.27 (d, J = 6.4 Hz, 3H, (CH 3 ) 2 CHCH(O)CH 3 ), 0.96 (d, J= 6.9 Hz, 6H, (CH 3 ) 2 CHCH(O)CH 3 ). 13 C{ 1 H} NMR (75.47 MHz, D 2 O, 298K) δ = (C=S), ((CH 3 ) 2 CHCH(O)CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ). IR = 2968, 1456, 1379, 1067, 1027 cm -1 Synthesis of xanthates XA1 and XA2 Methyl 2-((((3-methylbutan-2-yl)oxy)carbonothioyl)thio)propanoate XA1 C 10 H 18 O 3 S 2 M = g.mol -1 Methyl 2-bromopropionate (35.05 g, 0.21 mol) was added dropwise to a stirred solution of XA0 (40.5 g, 0.2 mol) in acetone (200 ml) at 0 C. After stirring for 3 h, the mixture was filtered off to remove the formed KBr. The solvent was concentrated under reduced pressure to yield a yellow oil (43.1 g, 86%). XA1 was used without additional purification. 1 H NMR ( MHz, CDCl 3, 298K) δ = (p, J = 6.3 Hz, 1H, (CH 3 ) 2 CHCH(O)CH 3 ), (m, 1H, CH(CH 3 )CO 2 CH 3 ), 3.74 (s, 3H, CO 2 CH 3 ), (m, 1H, (CH 3 ) 2 CHCH(O)CH 3 ), (dd, J = 7.4, 2.7 Hz, 3H, CH(CH 3 )CO 2 CH 3 ), (dd, J= 6.4, 4.9 Hz, 3H, (CH 3 ) 2 CHCH(O)CH 3 ), (dd, J= 6.9, 1.8 Hz, 6H, (CH 3 ) 2 CHCH(O)CH 3 ). 13 C{ 1 H} NMR (75.47 MHz, CDCl 3, 298K) δ = (C=S), (CO 2 CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), (CO 2 CH 3 ), (CH(CH 3 )CO 2 CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), (CH(CH 3 )CO 2 CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ). IR = 2966, 1741, 1241, 1161, 1046, 1024 cm -1 S5
6 Methyl 2-((((3-methylbutan-2-yl)oxy)carbonothioyl)thio)acetate XA2 C 9 H 16 O 3 S 2 M = g.mol -1 Methyl bromoacetate (35.1 g, 0.21 mol) was added dropwise to a stirred solution of XA0 (40.5 g, 0.2 mol) in acetone (200 ml) at 0 C. After stirring for 3 h, the mixture was filtered off to remove the formed KBr. The solvent was concentrated under reduced pressure to yield a yellow oil (42.2 g, 89%). XA2 was used without additional purification. 1 H NMR ( MHz, CDCl 3, 298K) δ = (m, 1H, (CH 3 ) 2 CHCH(O)CH 3 ), 3.87 (s, 2H, CH 2 CO 2 CH 3 ), 3.73 (s, 3H, CO 2 CH 3 ), (m, 1H, (CH 3 ) 2 CHCH(O)CH 3 ), (d, J = 6.4 Hz, 3H, (CH 3 ) 2 CHCH(O)CH 3 ), (d, J = 6.8 Hz, 6H, (CH 3 ) 2 CHCH(O)CH 3 ). 13 C{ 1 H} NMR (75.47 MHz, CDCl 3, 298K) δ = (C=S), (CO 2 CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), (CO 2 CH 3 ), (CH 2 CO 2 CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ). IR = 2964, 1743, 1242, 1157, 1048, 1024 cm -1 Synthesis of monoadducts M1-9 Methyl 2-methyl 4-((((3-methylbutan-2-yl)oxy) carbonothioyl)thio)nonanoate M1 O S S O O C 17 H 32 O 3 S 2 M = g.mol -1 XA1 (9.1 g, 36 mmol), 1-heptene (3.14 g, 32 mmol) and LPO (1.91 g, 4.8 mmol) were dissolved in toluene (5 ml) in a Schlenk tube. The solution was degassed with three freezepump-thaw cycles and sealed under vacuum. After heating and stirring during 16 h at 90 C, reaction mixture was purified with flash chromatography (SiO 2 ; petroleum ether/ethyl acetate 95:5). M1 was obtained as a yellow oil (10.3 g, 92%). S6
7 1 H NMR ( MHz, CDCl 3, 298K) δ = (m, 1H, (CH 3 ) 2 CHCH(O)CH 3 ), (m, 1H, SCHCH 2 CH(CH 3 )CO 2 CH 3 ), (m, 3H, CO 2 CH 3 ), (m, 1H, SCHCH 2 CH(CH 3 )CO 2 CH 3 ), (m, 2H, SCHCH 2 CH(CH 3 )CO 2 CH 3 ), (m, 3H, (CH 3 ) 2 CHCH(O)CH 3, CH 2 (CH 2 ) 3 CH 3 ), (m, 2H, CH 2 CH 2 (CH 2 ) 2 CH 3 ), (m, 7H, CH(CH 3 )CO 2 CH 3, (CH 2 ) 2 (CH 2 ) 2 CH 3 ), (m, 3H, (CH 3 ) 2 CHCH(O)CH 3 ), (m, 6H, (CH 3 ) 2 CHCH(O)CH 3 ), (m, 3H, (CH 2 ) 4 CH 3 ); 13 C{ 1 H} NMR (75.47 MHz, CDCl 3, 298K) δ = (C=S), (CO 2 CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), (CO 2 CH 3 ), (SCHCH 2 CH(CH 3 )CO 2 CH 3 ), (SCHCH 2 CH(CH 3 )CO 2 CH 3 ), (SCHCH 2 CH(CH 3 )CO 2 CH 3 ), (CH 2 (CH 2 ) 3 CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), ((CH 2 ) 2 CH 2 CH 2 CH 3 ), (CH 2 CH 2 (CH 2 ) 2 CH 3 ), ((CH 2 ) 3 CH 2 CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), (CH(CH 3 )CO 2 CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), (SCH(CH 2 ) 4 CH 3 ). IR = 2960, 2931, 2873, 1738, 1228, 1047, 1024 cm -1 HRMS (CI-CH4) calc. for [C 17 H 32 O 3 S 2 + H] + : Found Methyl 4-((((3-methylbutan-2-yl)oxy)carbonothioyl)thio)nonanoate M2 C 16 H 30 O 3 S 2 M = g.mol -1 XA2 (8.3 g, 37 mmol), 1-heptene (3.24 g, 33 mmol) and LPO (1.97 g, 4.95 mmol) were dissolved in toluene (5 ml) in a Schlenk tube. The solution was degassed with three freezepump-thaw cycles and sealed under vacuum. After heating and stirring during 16 h at 90 C, reaction mixture was purified with flash chromatography (SiO 2 ; petroleum ether/ethyl acetate 95:5). M2 was obtained as a yellow oil (10.1 g, 90%). S7
8 1 H NMR ( MHz, CDCl 3, 298K) δ = (p, J = 6.3 Hz, 1H, (CH 3 ) 2 CHCH(O)CH 3 ), (m, 1H, SCHCH 2 CH 2 CO 2 CH 3 ), 3.63 (s, 3H, CO 2 CH 3 ), (m, 2H, SCHCH 2 CH 2 CO 2 CH 3 ), (m, 2H, CH 2 (CH 2 ) 3 CH 3 ), (m, 1H, (CH 3 ) 2 CHCH(O)CH 3 ), (m, 2H, SCHCH 2 CH 2 CO 2 CH 3 ), (m, 2H, CH 2 CH 2 (CH 2 ) 2 CH 3 ), (m, 7H, (CH 2 ) 2 (CH 2 ) 2 CH 3, (CH 3 ) 2 CHCH(O)CH 3 ), (d, J = 6.8 Hz, 6H, (CH 3 ) 2 CHCH(O)CH 3 ), (m, 3H, (CH 2 ) 4 CH 3 ). 13 C{ 1 H} NMR (75.47 MHz, CDCl 3, 298K) δ = (C=S), (CO 2 CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), (CO 2 CH 3 ), (SCHCH 2 CH 2 CO 2 CH 3 ), (CH 2 (CH 2 ) 3 CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), ((CH 2 ) 2 CH 2 CH 2 CH 3 ), (SCHCH 2 CH 2 CO 2 CH 3 ), (SCHCH 2 CH 2 CO 2 CH 3 ), (CH 2 CH 2 (CH 2 ) 2 CH 3 ), ((CH 2 ) 3 CH 2 CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), ((CH 2 ) 4 CH 3 ). IR = 2959, 2929, 2857, 1741, 1228, 1049, 1024 cm -1 HRMS (CI-CH4) calc. for [C 16 H 30 O 3 S 2 + H] + : Found Methyl 5-(diethoxyphosphoryl)-2-methyl-4-((((3-methylbutan-2-yl) oxy)carbonothioyl)pentanoate M3 O S S P O O O O O C 17 H 33 O 6 PS 2 M = g.mol -1 XA1 (8.75 g, 35 mmol), DEAP (5.52 g, 31 mmol) and LPO (1.89 g, 4.7 mmol) were dissolved in toluene (5 ml) in a Schlenk tube. The solution was degassed with three freezepump-thaw cycles and sealed under vacuum. After heating and stirring during 16 h at 90 C, reaction mixture was purified with flash chromatography (SiO 2 ; dichloromethane/ethyl acetate 8:2). M3 was obtained as a yellow oil (11.9 g, 90%). 1 H NMR ( MHz, CDCl 3, 298K) δ = (m, 1H, (CH 3 ) 2 CHCH(O)CH 3 ), 4, (m, 4H, O=P(OCH 2 CH 3 ) 2 ), (m, 1H, CHS), 3.62 (s, 3H, CO 2 CH 3 ), (m, 6H, CH 2 P, (CH 3 ) 2 CHCH(O)CH 3, CH 2 CHCO 2 CH 3 ), (m, 9H, O=P(OCH 2 CH 3 ) 2, S8
9 CH 3 CHCO 2 CH 3 ), (m, 3H, (CH 3 ) 2 CHCH(O)CH 3 ), (m, 6H, (CH 3 ) 2 CHCH(O)CH 3 ). 13 C{ 1 H} NMR (75.47 MHz, CDCl 3, 298K) δ = (C=S), (CO 2 CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), (O=P(OCH 2 CH 3 ) 2 ), (CO 2 CH 3 ), (CHS), (CH 2 P), ((CH 3 ) 2 CHCH(O)CH 3 ), (CH 2 CH 2 CO 2 CH 3 ), (CHCO 2 CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), (CH 3 CHCO 2 CH 3 ), (O=P(OCH 2 CH 3 ) 2 ), ((CH 3 ) 2 CHCH(O)CH 3 ). 31 P{ 1 H} NMR ( MHz, CDCl 3, 298K) δ = 26.77, IR = 2975, 1735, 1238, 1042, 1026, 965, 842 cm -1 HRMS (CI-CH4) calc. for [C 17 H 33 O 6 PS 2 + H] + : Found Methyl 5-(diethoxyphosphoryl)-4-((((3-methylbutan-2-yl) oxy)carbonothioyl)pentanoate M4 C 16 H 31 O 6 PS 2 M = g.mol -1 XA2 (8.7 g, 37 mmol), DEAP (5.8 g, 33 mmol) and LPO (1.9 g, 4.95 mmol) were dissolved in toluene (5 ml) in a Schlenk tube. The solution was degassed with three freeze-pump-thaw cycles and sealed under vacuum. After heating and stirring during 16 h at 90 C, reaction mixture was purified with flash chromatography (SiO 2 ; dichloromethane/ethyl acetate 8:2). M4 was obtained as a yellow oil (12.1 g, 89%). 1 H NMR ( MHz, CDCl 3, 298K) δ = (m, 1H, (CH 3 ) 2 CHCH(O)CH 3 ), (m, 4H, O=P(OCH 2 CH 3 ) 2 ), (m, 1H, CHS), 3.55 (s, 3H, CO 2 CH 3 ), (m, 7H, CH 2 P, (CH 3 ) 2 CHCH(O)CH 3, CH 2 CH 2 CO 2 CH 3 ), (m, 6H, O=P(OCH 2 CH 3 ) 2 ), (m, 3H, (CH 3 ) 2 CHCH(O)CH 3 ), (m, 6H, (CH 3 ) 2 CHCH(O)CH 3 ). S9
10 13 C{ 1 H} NMR (75.47 MHz, CDCl 3, 298K) δ = (C=S), (CO 2 CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), (O=P(OCH 2 CH 3 ) 2 ), (CO 2 CH 3 ), (CHS), ((CH 3 ) 2 CHCH(O)CH 3 ), (CH 2 P), (CH 2 CH 2 CO 2 CH 3 ), (CH 2 CH 2 CO 2 CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), (O=P(OCH 2 CH 3 ) 2 ), ((CH 3 ) 2 CHCH(O)CH 3 ). 31 P{ 1 H} NMR ( MHz, CDCl 3, 298K) δ = 26.53, IR = 2977, 1738, 1238, 1045, 1025, 963, 842 cm -1 HRMS (CI-CH4) calc. for [C 16 H 31 O 6 PS 2 + H] + : Found Methyl 4-(dimethoxyphosphoryl)-2-methyl-4-((((3-methylbutan-2-yl) oxy)carbonothioyl)butanoate M5 C 14 H 27 O 6 PS 2 M = g.mol -1 XA1 (9.0 g, 36 mmol), DMVP (4.49 g, 33 mmol) and LPO (1.9 g, 4.95 mmol) were dissolved in toluene (5 ml) in a Schlenk tube. The solution was degassed with three freeze-pump-thaw cycles and sealed under vacuum. After heating and stirring during 16 h at 90 C, reaction mixture was stopped and purified with flash chromatography (SiO 2 ; dichloromethane/ethyl acetate 8:2). M5 was obtained as a yellow oil (10.1 g, 79%). 1 H NMR ( MHz, CDCl 3, 298K) δ = (m, 1H, (CH 3 ) 2 CHCH(O)CH 3 ), (m, 1H, CHP), (m, 6H, O=P(OCH 3 ) 2 ), (m, 3H, CO 2 CH 3 ), (m, 2H, CH 2 CH(CH 3 )CO 2 CH 3 ), (m, 1H, CH 2 CH(CH 3 )CO 2 CH 3 ), (m, 1H, (CH 3 ) 2 CHCH(O)CH 3 ), (m, 3H, (CH 3 ) 2 CHCH(O)CH 3 ), (m, 1H, CH 2 CH(CH 3 )CO 2 CH 3 ), (m, 6H, (CH 3 ) 2 CHCH(O)CH 3 ). 13 C{ 1 H} NMR (75.47 MHz, CDCl 3, 298K) δ = (C=S), (CO 2 CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), (O=P(OCH 3 ) 2 ), (CO 2 CH 3 ), (CHP), (CH 2 CH(CH 3 )CO 2 CH 3 ), (CH 2 CH(CH 3 )CO 2 CH 3 ), S10
11 ((CH 3 ) 2 CHCH(O)CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), (CH 2 CH(CH 3 )CO 2 CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ). 31 P{ 1 H} NMR ( MHz, CDCl 3, 298K) δ = 26.7, 26.6, 26.5, IR = 2955, 1736, 1243, 1035, 823 cm -1 HRMS (CI-CH4) calc. for [C 14 H 27 O 6 PS 2 + H] + : Found Methyl 4-(dimethoxyphosphoryl)-4-((((3-methylbutan-2-yl) oxy)carbonothioyl)butanoate M6 C 13 H 25 O 6 PS 2 M = g.mol -1 XA2 (14.2 g, 60 mmol), DMVP (2.72 g, 20 mmol) and LPO (1.2 g, 3 mmol) were introduced in a Schlenk tube. The solution was degassed with three freeze-pump-thaw cycles and sealed under vacuum. After heating and stirring during 5 h at 90 C, reaction mixture was stopped and purified with flash chromatography (SiO 2 ; ethyl acetate/petroleum ether 8:2) was used to recover the unreacted XA2 and (SiO 2 ; dichloromethane/ethyl acetate 8:2). M6 was obtained as a yellow oil (3.13 g, 42%). 1 H NMR ( MHz, CDCl 3, 298K) δ = (m, 1H, (CH 3 ) 2 CHCH(O)CH 3 ), (m, 1H, CHP), (m, 6H, O=P(OCH 3 ) 2 ), 3.59 (s, 3H, CO 2 CH 3 ), (m, 2H, CH 2 CH 2 CO 2 CH 3 ), (m, 2H, CH 2 CH 2 CO 2 CH 3 ), (m, 1H, (CH 3 ) 2 CHCH(O)CH 3 ), (m, 3H, (CH 3 ) 2 CHCH(O)CH 3 ), (m, 6H, (CH 3 ) 2 CHCH(O)CH 3 ). 13 C{ 1 H} NMR (75.47 MHz, CDCl 3, 298K) δ = (C=S), (CO 2 CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), (O=P(OCH 3 ) 2 ), (CO 2 CH 3 ), (CHP), ((CH 3 ) 2 CHCH(O)CH 3 ), (CH 2 CH 2 CO 2 CH 3 ), (CH 2 CH 2 CO 2 CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ). S11
12 31 P{ 1 H} NMR ( MHz, CDCl 3, 298K) δ = 26.3, IR = 2957, 1738, 1245, 1037, 830 cm -1 HRMS (CI-CH4) calc. for [C 13 H 25 O 6 PS 2 + H] + : Found Methyl 5,5,6,6,7,7,8,8,8-nonafluoro-2-methyl-4-((((3-methylbutan-2-yl) oxy)carbonothioyl)octanoate M7 C 16 H 21 F 9 O 3 S 2 M = g.mol -1 XA1 (4.47 g, 18 mmol), 1H, 1H, 2H-perfluoro-1-hexene (4.01 g, 16 mmol) and LPO (0.99 g, 2.5 mmol) were dissolved in toluene (5 ml) in a Schlenk tube. The solution was degassed with three freeze-pump-thaw cycles and sealed under vacuum. After heating and stirring during 16 h at 90 C, reaction mixture was purified with flash chromatography (SiO 2 ; hexane/ethyl acetate 95:5). M7 was obtained as a yellow oil (3.55 g, 45%). 1 H NMR ( MHz, CDCl 3, 298K) δ = (s, 1H, (CH 3 ) 2 CHCH(O)CH 3 ), (m, 1H, SCHCH 2 CH(CH 3 )), 3.66 (s, 3H, CO 2 CH 3 ), (m,1h, SCHCH 2 CH(CH 3 )), (m, 3H, (CH 3 ) 2 CHCH(O)CH 3 ); SCHCH 2 CH(CH 3 )), (m, 6H, (CH 3 ) 2 CHCH(O)CH 3 ; SCHCH 2 CH(CH 3 )), (m, 6H, (CH 3 ) 2 CHCH(O)CH 3 ). 13 C{ 1 H} NMR (75.47 MHz, CDCl 3, 298K) δ = (C=S), (CO 2 CH 3 ), (CH(CF 2 ) 3 CF 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), (CO 2 CH 3 ), CH(CF 2 ) 3 CF 3 ), (SCHCH 2 CH(CH 3 )), ((CH 3 ) 2 CHCH(O)CH 3 ), (SCHCH 2 CH(CH 3 )), ((CH 3 ) 2 CHCH(O)CH 3; (SCHCH 2 CH(CH 3 )). 19 F{ 1 H} NMR ( MHz, CDCl 3, 298K) δ = (CH(CF 2 ) 3 CF 3 )), (CH(CF 2 CF 2 CF 2 CF 3 )), (CH(CF 2 CF 2 CF 2 CF 3 )), (CH(CF 2 CF 2 CF 2 CF 3 )). S12
13 IR = 2974, 1740, 1238, 1215, 1135, 1043, 1023, 736 cm -1 HRMS (CI-CH4) calc. for [C 16 H 21 F 9 O 3 S 2 + H] + : Found Methyl 5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluoro-2-methyl -4-((((3-methylbutan-2-yl)oxy)carbonothioyl)dodecanoate M8 C 20 H 21 F 17 O 3 S 2 M = g.mol -1 XA1 (3.83 g, 16 mmol), 1H, 1H, 2H-perfluoro-1-decene (6.20 g, 14 mmol) and LPO (0.83 g, 2.1 mmol) were dissolved in toluene (5 ml) in a Schlenk tube. The solution was degassed with three freeze-pump-thaw cycles and sealed under vacuum. After heating and stirring during 16 h at 90 C, reaction mixture was purified with flash chromatography (SiO 2 ; hexane/ethyl acetate 9:1). M8 was obtained as a yellow oil (5.52 g, 56%). 1 H NMR ( MHz, CDCl 3, 298K) δ = (s, 1H, (CH 3 ) 2 CHCH(O)CH 3 ), (m, 1H, SCHCH 2 CH(CH 3 )), (m, 3H, CO 2 CH 3 ), (m,1h, SCHCH 2 CH(CH 3 )), (m, 1H, (CH 3 ) 2 CHCH(O)CH 3 ), (m, 2H, SCHCH 2 CH(CH 3 )), (m, 6H, (CH 3 ) 2 CHCH(O)CH 3 ; SCHCH 2 CH(CH 3 )), (m, 6H, (CH 3 ) 2 CHCH(O)CH 3 ). 13 C{ 1 H} NMR (75.47 MHz, CDCl 3, 298K) δ = (C=S), (CO 2 CH 3 ), (CH(CF 2 ) 7 CF 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), (CO 2 CH 3 ), (CH(CF 2 ) 3 CF 3 ), (SCHCH 2 CH(CH 3 )), ((CH 3 ) 2 CHCH(O)CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3; (SCHCH 2 CH(CH 3 )). 19 F{ 1 H} NMR ( MHz, CDCl 3, 298K) δ = (CH(CF 2 ) 7 CF 3 )), (CH(CF 2 (CF 2 ) 6 CF 3 )), (CH(CF 2 CF 2 (CF 2 )CF 3 )), (CH(CF 2 CF 2 (CF 2 ) 3 CF 2 CF 2 CF 3 )), (CH(CF 2 ) 5 CF 2 CF 2 CF 3 )), (CH(CF 2 ) 6 CF 2 CF 3 )). S13
14 IR = 2975, 1739, 1243, 1208, 1152, 1043, 1024, 910, 735 cm -1 HRMS (CI-CH4) calc. for [C 20 H 21 F 17 O 3 S 2 + H] + : Found Methyl 2-(4-((((3-methylbutan-2-yl)oxy)carbonothioyl)thio) -2,5-dioxo-1-phenylpyrrolidin-3-yl)propanoate M9 C 20 H 25 NO 5 S 2 M = g.mol -1 XA1 (9.43 g, 38 mmol), N-phenylmaleimide (6.07 g, 35 mmol) and LPO (2.00 g, 5 mmol) were dissolved in toluene (7 ml) in a Schlenk tube. The solution was degassed with three freeze-pump-thaw cycles and sealed under vacuum. After heating and stirring during 16 h at 90 C, reaction mixture was purified with flash chromatography (SiO 2 ; hexane/ethyl acetate 7:3). M9 was obtained as a yellow viscous oil (11.5 g, 78%). 1 H NMR ( MHz, CDCl 3, 298K) δ = (m, 5H, N-C 6 H 5 ), (s, 1H, (CH 3 ) 2 CHCH(O)CH 3 ), (m, 1H, SCH(CO)CH), (m, 3H, CO 2 CH 3 ), (m, 2H, SCH(CO)CH(CO)CH(CH 3 )), (1H, (CH 3 ) 2 CHCH(O)CH 3 ), (m, 3H, CH(CO)CH(CH 3 )), (m, 3H, (CH 3 ) 2 CHCH(O)CH 3 ), (m, 6H, (CH 3 ) 2 CHCH(O)CH 3 ). 13 C{ 1 H} NMR (75.47 MHz, CDCl 3, 298K) δ = (C=S), (C(O)NC(O) et CO 2 CH 3 ), ((CO) 2 N-C), ((CO) 2 N-C-C 5 H 5 ), ((CH 3 ) 2 CHCH(O)CH 3 ), (CO 2 CH 3 ), (SCH(CO)CH(CO)CH(CH 3 )), (SCH(CO)CH(CO)CH(CH 3 )), ((CH 3 ) 2 CHCH(O)CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ), ((CH 3 ) 2 CHCH(O)CH 3 ; SCH(CO)CH(CO)CH(CH 3 )). IR = 2964, 1784, 1718, 1597, 1382, 1245, 1192, 1045, 751 cm -1 HRMS (CI-CH4) calc. for [C 20 H 25 NO 5 S 2 + H] + : Found S14
15 Synthesis of thiolactones TL1-9 3-methyl-5-pentyldihydrothiophen-2(3H)-one TL1 C 10 H 18 OS M = g.mol -1 M1 (3.48 g, 10 mmol) was placed in a Schlenk tube, sealed under vacuum and immersed into dry bath maintained at 190 C. After heating during 15 min, it was cooled down and evacuated under vacuum to remove formed COS, 2-methylbut-2-ene and methanol, this cycle was reproduced 3 times. Then the reaction was heated during 48 h with periodical cooling down and evacuated to remove formed methanol. Finally, crude reaction was purified by flash chromatography (SiO 2 ; ethyl acetate/petroleum ether 9:1). TL1 was obtained as a colorless liquid (1.73 g, 93%). 1 H NMR (300 MHz, CDCl 3, 298K) δ = (m, 1H, SCHCH 2 CH), (m, 2H, SCHCH 2 CH), (m, 1H, SCHCH 2 CH), (m, 2H, CH 2 CH 2 (CH 2 ) 2 CH 3 ), (m, 2H, CH 2 (CH 2 ) 3 CH 3 ), (m, 4H, (CH 2 ) 2 (CH 2 ) 2 CH 3 ), (m, 3H, CHCH 3 ), (m, 3H, (CH 2 ) 4 CH 3 ). 13 C{ 1 H} NMR (75.47 MHz, CDCl 3, 298K) δ = (C=O), (SCHCH 2 CH), (SCHCH 2 CH), (SCHCH 2 CH), (CH 2 (CH 2 ) 3 CH 3 ) ((CH 2 ) 2 CH 2 CH 2 CH 3 ), (CH 2 CH 2 (CH 2 ) 2 CH 3 ), ((CH 2 ) 3 CH 2 CH 3 ), (CHCH 3 ), ((CH 2 ) 4 CH 3 ). IR = 2956, 2928, 2855, 1702, 1455, 954, 892 cm -1 HRMS (EI) calc. for [C 10 H 18 OS] +. : Found S15
16 5-pentyldihydrothiophen-2(3H)-one TL2 C 9 H 16 OS M = g.mol -1 M2 (3.35 g, 10 mmol) was placed in a Schlenk tube, sealed under vacuum and immersed into dry bath maintained at 190 C. After heating during 15 min it was cooled down and evacuated under vacuum to remove formed COS, 2-methylbut-2-ene and methanol, this cycle was reproduced 3 times. Then the reaction was heated during 48 h with periodical cooling down and evacuated to remove formed methanol. Finally, crude reaction was purified by flash chromatography (SiO 2 ; ethyl acetate/petroleum ether 9:1). TL2 was obtained as a colorless liquid (1.55 g, 90%). 1 H NMR ( MHz, CDCl 3, 298K) δ = (m, 1H, SCHCH 2 CH 2 ), (m, 2H, SCHCH 2 CH 2 ), (m, 2H, SCHCH 2 CH 2 ), (m, 2H, CH 2 CH 2 (CH 2 ) 2 CH 3 ), (m, 2H, CH 2 (CH 2 ) 3 CH 3 ), (m, 4H, (CH 2 ) 2 (CH 2 ) 2 CH 3 ), 0.86 (t,j = 7.0 Hz, 3H, (CH 2 ) 4 CH 3 ). 13 C{ 1 H} NMR (75.47 MHz, CDCl 3, 298K) δ = (C=O), (SCHCH 2 CH 2 ), (SCHCH 2 CH 2 ), (CH 2 (CH 2 ) 3 CH 3 ), ((CH 2 ) 2 CH 2 CH 2 CH 3 ), (SCHCH 2 CH 2 ), (CH 2 CH 2 (CH 2 ) 2 CH 3 ), ((CH 2 ) 3 CH 2 CH 3 ), ((CH 2 ) 4 CH 3 ). IR = 2956, 2927, 2856, 1705, 1456, 1153, 1038 cm -1 HRMS (EI) calc. for [C 9 H 16 OS] +. : Found S16
17 Diethyl((4-methyl-5-oxotetrahydrotiophen-2-yl)methyl)phosphonate TL3 C 10 H 19 O 4 PS M = g.mol -1 M3 (4.29 g, 10 mmol) was placed in a Schlenk tube, sealed under vacuum and immersed into a dry bath maintained at 190 C. After heating during 15 min it was cooled down and evacuated under vacuum to remove formed COS, 2-methylbut-2-ene and methanol, this cycle was reproduced 3 times. Then the reaction was heated during 1 h and finally cooled down and evacuated to remove formed methanol. Crude reaction was purified by flash chromatography (SiO 2 ; dichloromethane/ethyl acetate 8:2). TL3 was obtained as a colorless oil (2.4 g, 90%). 1 H NMR ( MHz, CDCl 3, 298K) δ = (m, 4H, O=P(OCH 2 CH 3 ) 2 ), (m, 1H, CHCH 2 P), (m, 2H, CH 2 CH(CH 3 )), (m, 2H, CHCH 2 P), (m, 1H, CHCH 2 P), (m, 6H, O=P(OCH 2 CH 3 ) 2 ), (m, 3H, CH 2 CH(CH 3 )). 13 C{ 1 H} NMR (75.47 MHz, CDCl 3, 298K) δ = (C=O), (O=P(OCH 2 CH 3 ) 2 ), (CHCH 2 P), (CH 2 CH(CH 3 )), (CH 2 CH(CH 3 )), (CHCH 2 P), (O=P(OCH 2 CH 3 ) 2 ), (CH 2 CH(CH 3 )). 31 P{ 1 H} NMR ( MHz, CDCl 3, 298K) δ = 26.40, IR = 2980, 2932, 2907, 2874, 1700, 1454, 1247, 1051, 1026, 964, 895 cm -1 HRMS (CI-CH4) calc. for [C 10 H 19 O 4 PS + H] + : Found S17
18 Diethyl((5-oxotetrahydrotiophen-2-yl)methyl)phosphonate TL4 C 9 H 17 O 4 PS M = g.mol -1 M4 (4.15 g, 10 mmol) was placed in a Schlenk tube, sealed under vacuum and immersed into a dry bath maintained at 190 C. After heating during 15 min it was cooled down and evacuated under vacuum to remove formed COS, 2-methylbut-2-ene and methanol, this cycle was reproduced 3 times. Then the reaction was heated during 1 h and finally cooled down and evacuated to remove formed methanol. Crude reaction was purified by flash chromatography (SiO 2 ; dichloromethane/ethyl acetate 8:2). TL4 was obtained as a colorless oil (2.3 g, 91%). 1 H NMR ( MHz, CDCl 3, 298K) δ = (m, 5H, CHCH 2 P, O=P(OCH 2 CH 3 ) 2 ), (m, 3H, CH 2 CH 2 CO, CH 2 CH 2 CO), (m, 2H, CHCH 2 P), (m, 1H, CH 2 CH 2 CO), (m, 6H, O=P(OCH 2 CH 3 ) 2 ). 13 C{ 1 H} NMR (75.47 MHz, CDCl 3, 298K) δ = (C=O), (O=P(OCH 2 CH 3 ) 2 ), (CHCH 2 P), (CH 2 CH 2 CO), (CHCH 2 P), (CH 2 CH 2 CO), (O=P(OCH 2 CH 3 ) 2 ). 31 P{ 1 H} NMR ( MHz, CDCl 3, 298K) δ = IR = 2982, 2907, 1704, 1251, 1051, 1026, 964, 807 cm -1 HRMS (CI-CH4) calc. for [C 9 H 17 O 4 PS + H] + : Found Dimethyl(4-methyl-5-oxotetrahydothiophen-2-yl)phosphonate TL5 C 7 H 13 O 4 PS M = g.mol -1 S18
19 M5 (3.86 g, 10 mmol) was placed in a Schlenk tube, sealed under vacuum and immersed into dry bath maintained at 190 C. After heating during 15 min it was cooled down and evacuated under vacuum to remove formed COS, 2-methylbut-2-ene and methanol, this cycle was reproduced 3 times. Then the reaction was heated during 1 h and finally cooled down and evacuated to remove formed methanol. Crude reaction was purified by flash chromatography (SiO 2 ; dichloromethane/ethyl acetate 8:2). TL5 was obtained as a colorless oil (1.9 g, 85%). 1 H NMR ( MHz, CDCl 3, 298K) δ = (m, 1H, CHP), (m, 6H, O=P(OCH 3 ) 2 ), (m, 2H, CH 2 ), (m, 1H, CHCH 3 ), (m, 3H, CHCH 3 ). 13 C{ 1 H} NMR (75.47 MHz, CDCl 3, 298K) δ = (C=O), (O=P(OCH 3 ) 2 ), (CHCH 3 ), (CHP), (CH 2 ), (CHCH 3 ). 31 P{ 1 H} NMR ( MHz, CDCl 3, 298K) δ = 26.8, IR = 2956, 1709, 1256, 1185, 1056, 1030, 956, 828 cm -1 HRMS (EI) calc. for [C 7 H 13 O 4 PS] +. : Found Dimethyl (5-oxotetrahydrothiophen-2-yl)phosphonate TL6 C 6 H 11 O 4 PS M = g.mol -1 M6 (3.73 g, 10 mmol) was placed in a Schlenk tube, sealed under vacuum and immersed into dry bath maintained at 190 C. After heating during 15 min it was cooled down and evacuated under vacuum to remove formed COS, 2-methylbut-2-ene and methanol, this cycle was reproduced 3 times. Then the reaction was heated during 1 h and finally cooled down and evacuated to remove formed methanol. Crude reaction was purified by flash chromatography (SiO 2 ; dichloromethane/ethyl acetate 8:2). TL6 was obtained as colorless oil (1.2 g, 57%). S19
20 1 H NMR ( MHz, CDCl 3, 298K) δ = (m, 1H, CHP), (m, 6H, O=P(OCH 3 ) 2 ), (m, 2H, CH 2 CH 2 CHP), (m, 2H, CH 2 CH 2 CHP). 13 C{ 1 H} NMR (75.47 MHz, CDCl 3, 298K) δ = (C=O), (O=P(OCH 3 ) 2 ), (CHP), (CH 2 CH 2 CHP), (CH 2 CH 2 CHP). 31 P{ 1 H} NMR ( MHz, CDCl 3, 298K) δ = IR = 2956, 2853, 1714, 1257, 1052, 1031, 831 cm -1 HRMS (CI-CH4) calc. for [C 6 H 11 O 4 PS] +. : Found methyl-5-(perfluorobutyl)dihydrotiophen-2(3H)-one TL7 C 9 H 7 F 9 OS M = g.mol -1 M7 (2.46 g, 5 mmol) was placed in a Schlenk tube, sealed under vacuum and immersed into a dry bath maintained at 190 C. After heating during 15 min it was cooled down and evacuated under vacuum to remove formed COS, 2-methylbut-2-ene and methanol, this cycle was reproduced 3 times. Then the reaction was heated during 72 h with periodical cooling down and evacuated to remove formed methanol. Finally, crude reaction was purified by flash chromatography (SiO 2 ; hexane/ethyl acetate 95:5). TL7 was obtained as a colorless liquid (1.1 g, 68%). 1 H NMR ( MHz, CDCl 3, 298K) δ = (m, 1H, CHCF 2 ), (m, 2H, C(O)CH(CH 3 )CH 2 CH), (dd, J = 12.1, 10.9 Hz 1H, C(O)CH(CH 3 )), (d, J = 6.5 Hz, 3H, C(O)CH(CH 3 )). 13 C{ 1 H} NMR (75.47 MHz, CDCl 3, 298K) δ = (C=O), (CH(CF 2 ) 3 CF 3 ), (CH(CF 2 ) 3 CF 3 ), (C(O)CH(CH 3 )), (C(O)CH(CH 3 )CH 2, (C(O)CH(CH 3 )CH 2 ). S20
21 19 F{ 1 H} NMR ( MHz, CDCl 3, 298K) δ = (CH(CF 2 ) 3 CF 3 )), (CH(CF 2 (CF 2 ) 2 CF 3 )), (CH(CF 2 -CF 2 -CF 2 -CF 3 )), (CH(CF 2 -CF 2 -CF 2 -CF 3 )). IR = 2979, 1720, 1534, 1222, 1235, 1172, 1135, 1140, 963, 906, 735 cm -1 HRMS (CI-CH4) calc. for [C 9 H 7 F 9 OS + H] + : Found methyl-5-(perfluorooctyl)dihydrotiophen-2(3H)-one TL8 C 13 H 7 F 17 OS M = g.mol -1 M8 (5.49 g, 7.9 mmol) was placed in a Schlenk tube, sealed under vacuum and immersed into dry bath maintained at 190 C. After heating during 15 min it was cooled down and evacuated under vacuum to remove formed COS, 2-methylbut-2-ene and methanol, this cycle was reproduced 3 times. Then the reaction was heated during 48 h with periodical cooling down and evacuated to remove formed methanol. Finally, crude reaction was purified by flash chromatography (SiO 2 ; hexane/ethyl acetate 95:5). TL8 was obtained as a white solid (2.58 g, 61%). 1 H NMR ( MHz, CDCl 3, 298K) δ = (m, 1H, CHCF 2 ), (m, 2H, C(O)CH(CH 3 )CH 2 CH) ), (m, 1H, C(O)CH(CH 3 )CH 2 CH), (m, 3H, C(O)CH(CH 3 )). 13 C{ 1 H} NMR (75.47 MHz, CDCl 3, 298K) δ = (C=O), (CH(CF 2 ) 3 CF 3 ), (CH(CF 2 ) 3 CF 3 ), (C(O)CH(CH 3 )), (C(O)CH(CH 3 )CH 2, (C(O)CH(CH 3 )CH 2 ). S21
22 19 F{ 1 H} NMR ( MHz, CDCl 3, 298K) δ = (CH(CF 2 ) 7 CF 3 )), (CH(CF 2 (CF 2 ) 6 CF 3 )), (CH(CF 2 CF 2 (CF2) 5 CF 3 )), (CH(CF 2 CF 2 (CF 2 ) 3 CF 2 CF 2 CF 3 )), (CH(CF 2 ) 5 CF 2 CF 2 CF 3 )), (CH(CF 2 ) 6 CF 2 CF 3 )). IR = 2976, 1717, 1221, 2202, 1148, 1114, 971 cm -1 HRMS (CI-CH4) calc. for [C 13 H 7 F 17 OS + H] + : Found methyl-5-phenyldihydro-2H-thieno[2,3-c]pyrrole-2,4,6(3H,5H)-trione TL9 C 13 H 11 NO 3 S M = g.mol -1 M9 (11.4 g, 27 mmol) was placed in a Schlenk tube, sealed under vacuum and immersed into dry bath maintained at 190 C. After heating during 15 min it was cooled down and evacuated under vacuum to remove formed COS, 2-methylbut-2-ene and methanol, this cycle was reproduced 3 times. Then the reaction was heated during 48 h with periodical cooling down and evacuated to remove formed methanol. Finally, crude reaction was purified by flash chromatography (SiO 2 ; hexane/ethyl acetate 6:4). TL9 was obtained as a brown pale solid (4.1 g, 59%). 1 H NMR ( MHz, CDCl 3, 298K) δ = (m, 5H, N-C 6 H 5 ) (d,j = 8.3 Hz, 1H, SCH(CO)CH), (m, 1H, CH(CH 3 )CHC(O)), (m, 1H, C(O)CH(CH 3 )), (d,j = 7.4 Hz, 3H, C(O)CH(CH 3 )). 13 C{ 1 H} NMR (75.47 MHz, CDCl 3, 298K) δ = (SC=O), (C(O)NC(O)), (N-C 6 H 5 ), (SCH(CO)), (C(O)CH(CH 3 )), (C(O)CH(CH 3 )CH(CO), (C(O)CH(CH 3 )CH 2 ). IR = 2974, 1786, 1713, 1596, 1495, 1386, 1191 cm -1 HRMS (CI-CH4) calc. for [C 13 H 11 NO 3 S + H] + : Found S22
23 NMR Spectra: 1 H NMR ( MHz, CDCl 3, 298K) Figure S1. 1 H NMR spectrum of DEAP. 13 C NMR (75.47 MHz, CDCl 3, 298K) Figure S2. 13 C NMR spectrum of DEAP. S23
24 31 P NMR ( MHz, CDCl 3, 298K) Figure S3. 31 P NMR spectrum of DEAP. 1 H NMR ( MHz, D2O, 298K) Figure S4. 1 H NMR spectrum of XA0. S24
25 13 C NMR (75.47 MHz, D2O, 298K) Figure S5. 13 C NMR spectrum of XA0. 1 H NMR ( MHz, CDCl 3, 298K) Figure S6. 1 H NMR spectrum of XA1. S25
26 13 C NMR (75.47 MHz, CDCl 3, 298K) Figure S7. 13 C NMR spectrum of XA1. 1 H NMR ( MHz, CDCl 3, 298K) Figure S8. 1 H NMR spectrum of XA2. S26
27 13 C NMR (75.47 MHz, CDCl 3, 298K) Figure S9. 13 C NMR spectrum of XA2. 1 H NMR ( MHz, CDCl 3, 298K) Figure S10. 1 H NMR spectrum of M1. S27
28 13 C NMR (75.47 MHz, CDCl 3, 298K) Figure S C NMR spectrum of M1. 1 H NMR ( MHz, CDCl 3, 298K) Figure S12. 1 H NMR spectrum of M2. S28
29 13 C NMR (75.47 MHz, CDCl 3, 298K) Figure S C NMR spectrum of M2. 1 H NMR ( MHz, CDCl 3, 298K) Figure S14. 1 H NMR spectrum of M3. S29
30 13 C NMR (75.47MHz, CDCl 3, 298K) Figure S C NMR spectrum of M3. 31 P NMR (121.49MHz, CDCl 3, 298K) Figure S P NMR spectrum of M3. S30
31 O S S P O O O O O 1 H NMR ( MHz, CDCl 3, 298K) Figure S17. 1 H NMR spectrum of M4. 13 C NMR (75.47 MHz, CDCl 3, 298K) Figure S C NMR spectrum of M4. S31
32 O S S P O O O O O 31 P NMR ( MHz, CDCl 3, 298K) Figure S P NMR spectrum of M4. 1 H NMR ( MHz, CDCl 3, 298K) Figure S20. 1 H NMR spectrum of M5. S32
33 13 C NMR (75.47 MHz, CDCl 3, 298K) Figure S C NMR spectrum of M5. 31 P NMR ( MHz, CDCl 3, 298K) Figure S P NMR spectrum of M5. S33
34 Figure S P NMR spectrum of DMVP oligomers obtained after 16 h reaction time. 1 H NMR ( MHz, CDCl 3, 298K) Figure S24. 1 H NMR spectrum of M6. S34
35 13 C NMR (75.47 MHz, CDCl 3, 298K) Figure S C NMR spectrum of M6. 31 P NMR ( MHz, CDCl 3, 298K) Figure S P NMR spectrum of M6. S35
36 1 H NMR ( MHz, CDCl 3, 298K) Figure S27. 1 H NMR spectrum of M7. 13 C NMR (75.47 MHz, CDCl 3, 298K) Figure S C NMR spectrum of M7. S36
37 19 F NMR ( MHz, CDCl 3, 298K) Figure S F NMR spectrum of M7. 1 H NMR ( MHz, CDCl 3, 298K) Figure S30. 1 H NMR spectrum of M8. S37
38 13 C NMR (75.47 MHz, CDCl 3, 298K) Figure S C NMR spectrum of M8. 19 F NMR ( MHz, CDCl 3, 298K) Figure S F NMR spectrum of M8. S38
39 1 H NMR ( MHz, CDCl 3, 298K) Figure S33. 1 H NMR spectrum of M9. 13 C NMR (75.47 MHz, CDCl 3, 298K) Figure S C NMR spectrum of M9. S39
40 1 H NMR ( MHz, CDCl 3, 298K) Figure S35. 1 H NMR spectrum of TL1. 13 C NMR (75.47 MHz, CDCl 3, 298K) Figure S C NMR spectrum of TL1. S40
41 1 H NMR ( MHz, CDCl 3, 298K) Figure S37. 1 H NMR spectrum of TL2. 13 C NMR (75.47 MHz, CDCl 3, 298K) Figure S C NMR spectrum of TL2. S41
42 1 H NMR ( MHz, CDCl 3, 298K) Figure S39. 1 H NMR spectrum of TL3. 13 C NMR (75.47 MHz, CDCl 3, 298K) Figure S C NMR spectrum of TL3. S42
43 31 P NMR ( MHz, CDCl 3, 298K) Figure S P NMR spectrum of TL3. 1 H NMR ( MHz, CDCl 3, 298K) Figure S42. 1 H NMR spectrum of TL4. S43
44 13 C NMR (75.47 MHz, CDCl 3, 298K) Figure S C NMR spectrum of TL4. 31 P NMR ( MHz, CDCl 3, 298K) Figure S P NMR spectrum of TL4. S44
45 1 H NMR ( MHz, CDCl 3, 298K) Figure S45. 1 H NMR spectrum of TL5. 13 C NMR (75.47 MHz, CDCl 3, 298K) Figure S C NMR spectrum of TL5. S45
46 31 P NMR ( MHz, CDCl 3, 298K) Figure S P NMR spectrum of TL5. 1 H NMR ( MHz, CDCl 3, 298K) Figure S48. 1 H NMR spectrum of TL6. S46
47 13 C NMR (75.47 MHz, CDCl 3, 298K) Figure S C NMR spectrum of TL6. 31 P NMR ( MHz, CDCl 3, 298K) Figure S P NMR spectrum of TL6. S47
48 1 H NMR ( MHz, CDCl 3, 298K) Figure S51. 1 H NMR spectrum of TL7. O S CF 2 F 2 C CF 2 F 3 C 13 C NMR (75.47 MHz, CDCl 3, 298K Figure S C NMR spectrum of TL7. S48
49 19 F NMR ( MHz, CDCl 3, 298K) Figure S F NMR spectrum of TL7. 1 H NMR ( MHz, CDCl 3, 298K) Figure S54. 1 H NMR spectrum of TL8. S49
50 13 C NMR (75.47 MHz, CDCl 3, 298K) Figure S C NMR spectrum of TL8. 19F NMR ( MHz, CDCl 3, 298K) Figure S F NMR spectrum of TL8. S50
51 1 H NMR ( MHz, CDCl 3, 298K) Figure S57. 1 H NMR spectrum of TL9. 13 C NMR (75.47 MHz, CDCl 3, 298K) Figure S C NMR spectrum of TL9. S51
52 General procedures of polymer end-functionalizations Mono-functionalization: Typically, 200 mg (0.1 mmol) of MPEG-NH 2, thiolactone TL1 or TL5 (0.1 mmol) and 15 mg (0.1 mmol) of benzyl acrylate were placed in a Schlenk tube with a stir bar. The mixture was heated at 50 C under stirring with a dry bath during 6 h. The crude reaction mixture was analyzed by NMR, SEC and MALDI-TOF MS techniques. - 1 H and 31 P NMR analyses a b b CHCl 3 b b b b a Figure S59. 1 H NMR spectrum of the MPEG-NH 2 / TL5 / BzA crude product ( MHz, CDCl 3 ). b) a) Figure S P NMR spectra of a) thiolactone TL5 and b) MPEG-NH 2 / TL5 / BzA crude product ( MHz, CDCl 3 ). S52
53 - SEC chromatograms a) MPEG-NH 2 MPEG-NH 2 / TL5 / BzA b) MPEG-NH 2 MPEG-NH 2 / TL1 / BzA M n = 3570 g.mol -1 M n = 2920 g.mol -1 M n = 3420 g.mol -1 M n = 2920 g.mol Elution time (min) Elution time (min) Figure S61. a) SEC analysis (RI traces) of MPEG-NH 2 and corresponding end-functionalized product with TL5 and BzA; b) SEC analysis (RI traces) of MPEG-NH 2 and corresponding end-functionalized product with TL1 and BzA. S53
54 - MALDI-TOF MS spectra a) n= 41 [M A +Na + ] n= 37 A B n= 47 0 n= 32 n= 53 b) [M A + Na + ] (n= 40) [M A + Na + ] (n= 41) m/z = 44 m/z = 44 [M B + Na + ] (n= 41) [M B + Na + ] (n= 42) [M A + K + ] (n= 40) [M A + K + ] (n= 41) Figure S62. a) MALDI-TOF MS spectrum of commercially available methoxypoly(ethylene glycol) amine (MPEG-NH 2 ); b) Zoom between 1850 and 1970 m/z of spectrum a). S54
55 a) n = 36 [M B + Na + ] A B n = 38 [M A + Na + ] b) [M B + Na + ] (n= 34) [M B + Na + ] (n= 35) [M B + Na + ] (n= 36) m/z = 44 m/z = 44 [M A + Na + ] (n= 34) [M B + K + ] (n= 34) [M A + Na + ] (n= 35) [M B + K + ] (n= 35) [M A + K + ] (n= 34) [M A + K + ] (n= 35) Figure S63. a) MALDI-TOF MS spectrum of MPEG-NH 2 end-functionalized with TL1 and BzA ; b) Zoom between 1930 and 2030 m/z of spectrum a). S55
56 Bi-functionalizations: Typically, MPEG-NH 2, PEG-diNH 2, or PDMS-diNH 2 (0.12 mmol), thiolactone (0.24 mmol) and acrylate compounds (0.24 mmol) were placed in a Schlenk tube with a stir bar. The mixture was stirred and heated at 50 C with a dry bath during 6 h. The crude reaction mixture was analyzed by NMR, SEC and MALDI-TOF MS techniques. - MALDI-TOF MS spectra A A n= 31 n= 32 B n= 30 A n= 31 n= 33 m/z= 44 m/z= 44 n= 36 B m/z= 44 n= 25 B n= 40 n= 19 Figure S64. MALDI-TOF MS spectrum of commercially available poly(ethylene glycol) PEG-diNH 2. S56
57 n= 28 n= 29 n= 30 n= 33 n= 29 n= 30 m/z = 44 n= 25 n= 9 n= 36 n= 6 n= 39 Figure S65. MALDI-TOF MS spectrum of PEG-diNH 2 end-functionalized with TL5 and BzA. 0 n= 12 n= 13 n= 14 n= 15 m/z= 74 m/z = 74 n= 7 [M+Na + ] n= 8 n= 9 m/z = 74 n= 10 n= 11 n= 12 n= 15 Figure S66. MALDI-TOF MS spectrum of commercially available PDMS-diNH 2. S57
58 n= 0 [M+Na + ] n= 1 n= 0 n= 1 m/z= 74 n= 2 n= 2 m/z= 74 n= 3 n= 4 n= 5 Figure S67. MALDI-TOF MS spectrum of PDMS end-functionalized with TL4 and BzA n= 0 [M+Na + ] n= 1 n= 2 n= 3 n= 2 m/z= 74 n= 4 m/z= 74 n= 3 n= 4 n= 5 Figure S68. MALDI-TOF MS spectrum of PDMS end-functionalized with TL5 and BzA. S58
59 n= 0 [M+Na + ] n= 1 n= 1 n= 2 m/z = 74 n= 2 n= 3 n= 3 m/z= 74 n= 4 n= 5 Figure S69. MALDI-TOF MS spectrum of PDMS end-functionalized with TL5 and MA. n= 0 [M+Na + ] n= 1 n= 1 n= 2 m/z= 74 n= 3 n= 2 m/z= 74 n= 3 n= 4 n= 5 Figure S70. MALDI-TOF MS spectrum of PDMS end-functionalized with TL5 and TFOA. S59
60 n= 0 [M+Na + ] n= 1 n= 1 n= 2 m/z= 74 n= 2 m/z= 74 n= 3 n= 4 n= 3 n= 4 n= 5 Figure S71. MALDI-TOF MS spectrum of PDMS end-functionalized with TL7 and BzA. n= 0 [M+Na + ] n= 1 n= 0 n= 1 n= 2 n= 2 n= 3 m/z= 74 m/z= 74 n= 3 n= 4 n= 5 Figure S72. MALDI-TOF MS spectrum of PDMS end-functionalized with TL9 and BzA. S60
61 Step-growth polymerization Synthetic procedure: In a Schlenk tube, 704 mg (0.28 mol) of PDMS-diNH 2, 100 mg (0.48 mol) of thiolactone TL 5 and 111 mg (0.19 mol) of poly(ethylene glycol) diacrylate were introduced. The reaction mixture was then stirred and heated at 50 C with a dry bath. Aliquots were taken at 15 min, 30 min, 1 h, 2 h, 4 h and 6 h to determine monomer conversion by 1 H and 31 P NMR. Number average molecular weight M n and dispersity (Ð) were determined by SEC analyses in THF CHCl 3 8, 12, h , 7 2 7, 9, min 0 min Figure S73. 1 H NMR spectra of the functional polymer obtained by step-growth polymerization between PDMS-diNH 2, TL5 and PEG-diacrylate at t = 0 min, 15 min and 4 h reaction time ( MHz, CDCl 3,). S61
62 Table S1. Characterization data of PDMS-diNH 2 /TL5/PEG-diacrylate step-growth polymerization at different reaction times. Entry Reaction time (h) Conv. 1 H NMR a M n b (%) (g.mol -1 ) a determined by 1 H NMR from acrylate signal, b determined by SEC analysis in THF with PS standard. Ð b S62
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