Elijah T. Marris et al. “A proline-based redox–release platform for programmed access to diverse sulfur(VI) and fluoroalkyl radicals.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.15007588/v1

Alkene
Identifier S1
¹H NMR (CDCl₃, 500 MHz) δ 7.64 – 7.57 (m, 2H), 7.44 (m, 3H), 5.66 (ddt, J = 18.0, 9.4, 6.6 Hz, 1H), 5.05 – 5.03 (m, 1H), 5.01 (s, 1H), 4.24 (t, J = 6.5 Hz, 2H), 2.72 (s, 3H), 2.38 – 2.29 (m, 2H)
HRMS (ESI) m/z calcd. for C₁₅H₁₅NO₃ [M+H]⁺ : 258.1125, found: 258.1122
SI, p. S1-3
Alkene
Identifier S2
¹H NMR (CDCl₃, 500 MHz) δ 8.01 (d, J = 8.7 Hz, 2H), 6.91 (d, J = 8.7 Hz, 2H), 6.49 (dd, J = 14.3, 6.7 Hz, 1H), 4.45 (t, 2H), 4.19 (dd, J = 14.3, 2.1 Hz, 1H), 4.00 (dd, J = 6.8, 2.2 Hz, 1H), 3.84 (m, 7H), 3.79 – 3.76 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 166.4, 163.5, 151.8, 151.8, 131.8, 122.6, 113.7, 86.9, 69.7, 69.6, 67.4, 63.9, 55.5
HRMS (ESI) m/z calcd. for C₁₄H₁₈O₅ [M+H]⁺ : 267.1227, found: 267.1222
SI, p. S1-4
Alkene
Identifier S3
¹H NMR (CDCl₃, 500 MHz) δ 7.94 (d, J = 8.0 Hz, 2H), 7.22 (d, J = 7.9 Hz, 2H), 6.50 (dd, J = 14.3, 6.7 Hz, 1H), 4.56 – 4.50 (m, 2H), 4.23 (dd, J = 14.3, 2.3 Hz, 1H), 4.05 (dt, J = 6.9, 1.4 Hz, 1H), 4.00 (t, 2H), 2.39 (s, 3H)
¹³C NMR (CDCl₃, 125 MHz) δ 166.6, 151.7, 151.7, 143.9, 129.9, 129.2, 127.3, 87.2, 66.1, 63.1, 21.7
HRMS (ESI) m/z calcd. for C₁₂H₁₄O₃ [M+H]⁺ : 207.1016, found: 207.1014
SI, p. S1-4
Alkene
Identifier S4
¹H NMR (CDCl₃, 500 MHz) δ 7.12 (d, J = 8.6 Hz, 2H), 6.83 (d, J = 8.5 Hz, 2H), 5.64 (s, 2H), 4.26 (t, J = 7.0 Hz, 2H), 3.77 (s, 3H), 3.08 (p, J = 8.2 Hz, 1H), 2.87 (t, J = 7.0 Hz, 2H), 2.61 (d, J = 8.2 Hz, 4H)
¹³C NMR (CDCl₃, 125 MHz) δ 176.2, 158.4, 130.0, 129.1, 114.0, 65.3, 55.3, 41.7, 36.4, 34.4
HRMS (ESI) m/z calcd. for C₁₅H₁₈O₃ [M+Na]⁺ : 269.1148, found: 269.1145
SI, p. S1-4
Alkene
Identifier S5
¹H NMR (CDCl₃, 500 MHz) δ 7.77 (d, J = 8.6 Hz, 2H), 7.47 (d, J = 8.6 Hz, 2H), 7.16 (d, J = 7.8 Hz, 2H), 7.09 (d, J = 8.2 Hz, 2H), 6.74 (s, 1H), 5.73 (ddt, J = 17.0, 10.1, 6.7 Hz, 1H), 5.12 – 5.03 (m, 2H), 3.08 (t, J = 7.3 Hz, 2H), 2.74 (s, 3H), 2.37 (s, 3H), 2.33 – 2.24 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 145.4, 144.4, 144.1, 142.6, 140.0, 137.6, 134.4, 129.9, 128.9, 128.4, 125.8, 125.7, 122.3, 120.1, 117.5, 49.8, 34.9, 32.4, 21.5, 0.1
¹⁹F NMR (CDCl₃, 376 MHz) δ -62.4
HRMS (ESI) m/z calcd. for C₂₂H₂₂F₃N₃O₂S [M+H]⁺ : 450.1458, found: 450.1453
SI, p. S1-5
Styrene oxide
Identifier S6
¹H NMR (400 MHz, CDCl₃) δ 8.05 (d, J = 8.3 Hz, 1H), 7.36 (d, J = 8.3 Hz, 2H), 6.11 – 5.97 (m, 1H), 5.46 – 5.36 (m, 1H), 4.83 (dt, J = 5.7, 1.5 Hz, 2H), 3.91 (dd, J = 4.2, 2.5 Hz, 1H), 3.19 (dd, J = 5.5, 4.1 Hz, 1H), 2.79 (dd, J = 5.6, 2.5 Hz, 1H)
SI, p. S1-5
Benzoic acid
Identifier S7
¹H NMR (500 MHz, DMSO-d₆) δ 7.53 (dd, J = 7.6, 1.1 Hz, 2H), 7.45 (dd, J = 2.5, 1.5 Hz, 2H), 7.40 (t, J = 7.9 Hz, 1H), 7.20 (ddd, J = 8.2, 2.6, 0.8 Hz, 3H), 6.04 (ddt, J = 17.2, 10.4, 5.1 Hz, 1H), 5.40 (dq, J = 17.3, 1.6 Hz, 1H), 5.27 (dq, J = 10.5, 1.4 Hz, 2H), 4.62 (dt, J = 5.0, 1.4 Hz, 3H)
SI, p. S1-5
S(VI)-Pro-OH derivative
Identifier S(VI)-Pro-OH1
¹H NMR (CDCl₃, 500 MHz) δ 8.02 (d, J = 8.0 Hz, 2H), 7.81 (d, J = 8.0 Hz, 2H), 4.39 (dd, J = 7.2, 5.4 Hz, 1H), 3.51 (ddd, J = 9.0, 7.5, 4.5 Hz, 1H), 3.36 (dt, J = 9.0, 7.3 Hz, 1H), 2.14 (dt, J = 12.6, 6.8 Hz, 2H), 2.02 (dq, J = 13.2, 8.0, 7.8 Hz, 1H), 1.92 – 1.83 (m, 1H)
¹³C NMR (CDCl₃, 125 MHz) δ 177.2, 141.8, 135.0, 134.8, 134.5, 134.3, 128.0, 126.5, 126.4, 126.3, 126.3, 126.3, 124.3, 122.2, 120.0, 60.3, 48.5, 30.9, 24.7
¹⁹F NMR (CDCl₃, 376 MHz) δ -63.1
HRMS (ESI) m/z calcd. for C₁₂H₁₂F₃NO₄S [M−H]⁻ : 322.0366, found: 322.0365
SI, p. S1-6
S(VI)-Pro-OH derivative
Identifier S(VI)-Pro-OH2
¹H NMR (CDCl₃, 500 MHz) δ 7.84 – 7.80 (m, 2H), 7.04 – 6.99 (m, 2H), 4.24 (dd, J = 8.2, 3.5 Hz, 1H), 3.89 (s, 3H), 3.54 – 3.48 (m, 1H), 3.24 (dt, J = 9.3, 7.4 Hz, 1H), 2.25 – 2.15 (m, 1H), 1.98 – 1.86 (m, 2H), 1.80 – 1.70 (m, 1H)
¹³C NMR (CDCl₃, 125 MHz) δ 174.4, 163.7, 130.0, 128.5, 114.6, 60.7, 55.8, 49.2, 30.4, 24.8
HRMS (ESI) m/z calcd. for C₁₂H₁₅NO₅S [M−H]⁻: 284.0598, found: 284.0601
SI, p. S1-7
S(VI)-Pro-OH derivative
Identifier S(VI)-Pro-OH3
¹H NMR (CDCl₃, 500 MHz) δ 7.96 – 7.88 (m, 2H), 7.22 (t, J = 8.5 Hz, 2H), 4.32 (dd, J = 8.5, 3.7 Hz, 1H), 3.50 (ddd, J = 9.4, 7.1, 4.4 Hz, 1H), 3.30 (dt, J = 9.4, 7.3 Hz, 1H), 2.16 (ddt, J = 12.1, 6.2, 4.0 Hz, 1H), 2.09 – 1.94 (m, 2H), 1.88 – 1.78 (m, 1H)
¹³C NMR (CDCl₃, 125 MHz) δ 176.0, 166.6, 164.6, 134.0, 133.9, 130.5, 130.4, 116.7, 116.5, 60.4, 48.8, 30.8, 24.8
¹⁹F NMR (CDCl₃, 376 MHz) δ -104.4
HRMS (ESI) m/z calcd. for C₁₁H₁₂FNO₄S [M−H]⁻: 272.0398, found: 272.0399
SI, p. S1-7
S(VI)-Pro-OH derivative
Identifier S(VI)-Pro-OH4
¹H NMR (Acetone-d₆, 500 MHz) δ 11.16 (s, 1H), 9.03 (d, J = 2.3 Hz, 1H), 8.83 (dd, J = 4.8, 1.6 Hz, 1H), 8.25 (dt, J = 8.1, 1.9 Hz, 1H), 7.63 (ddd, J = 8.1, 4.7, 0.9 Hz, 1H), 4.38 (dd, J = 8.7, 3.7 Hz, 1H), 3.48 (ddd, J = 9.4, 7.3, 4.7 Hz, 1H), 3.39 (dt, J = 9.3, 7.1 Hz, 1H), 2.15 (dtd, J = 12.4, 8.8, 7.2 Hz, 1H), 2.07 – 1.91 (m, 2H), 1.83 (dtt, J = 12.0, 7.1, 4.4 Hz, 1H)
¹³C NMR (Acetone-d₆, 125 MHz) δ 173.2, 154.2, 148.8, 136.3, 136.0, 124.9, 61.4, 49.2, 31.6, 25.3
HRMS (ESI) m/z calcd. for C₁₀H₁₂N₂O₄S [M+H]⁺: 257.0591, found: 257.0587
SI, pp. S1-7–S1-8
S(VI)-Pro-OH derivative
Identifier S(VI)-Pro-OH5
¹H NMR (CDCl₃, 500 MHz) δ 4.37 (dd, J = 8.6, 3.6 Hz, 1H), 3.52 (ddd, J = 9.0, 7.4, 4.4 Hz, 1H), 3.45 (dt, J = 9.0, 7.3 Hz, 1H), 2.65 (s, 3H), 2.42 (s, 3H), 2.32 – 2.24 (m, 1H), 2.24 – 2.16 (m, 1H), 2.13 – 2.04 (m, 1H), 2.04 – 1.94 (m, 1H)
¹³C NMR (CDCl₃, 125 MHz) δ 176.0, 173.9, 158.0, 115.5, 59.6, 48.4, 31.1, 24.7, 12.9, 11.1
HRMS (ESI) m/z calcd. for C₁₀H₁₄N₂O₅S [M+H]⁺: 275.0696, found: 275.0693
SI, p. S1-8
S(VI)-Pro-OH derivative
Identifier S(VI)-Pro-OH6
¹H NMR (CDCl₃, 500 MHz) δ 4.52 (dd, J = 8.7, 3.7 Hz, 1H), 3.53 (t, J = 6.7 Hz, 2H), 2.60 – 2.48 (m, 1H), 2.30 (dq, J = 12.6, 8.3 Hz, 1H), 2.20 (ddd, J = 13.3, 6.6, 4.4 Hz, 1H), 2.04 (dtt, J = 8.3, 6.2, 3.6 Hz, 2H), 1.28 – 1.14 (m, 2H), 1.07 – 0.92 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 176.9, 60.4, 48.4, 30.7, 28.7, 25.1, 5.4, 4.7
HRMS (ESI) m/z calcd. for C₈H₁₃NO₄S [M−H]⁻: 218.0493, found: 218.0488
SI, p. S1-8
S(VI)-Pro-RAE derivative
Identifier Ts-Pro-RAE
¹H NMR (CDCl₃, 500 MHz) δ 7.89 (dd, J = 5.4, 3.0 Hz, 2H), 7.84 – 7.78 (m, 4H), 7.33 – 7.30 (m, 2H), 4.80 (dd, J = 8.8, 3.2 Hz, 1H), 3.50 – 3.40 (m, 2H), 2.41 (s, 3H), 2.36 (ddt, J = 12.8, 7.2, 3.7 Hz, 1H), 2.27 (dtd, J = 12.8, 9.3, 9.2, 7.1 Hz, 1H), 2.13 – 2.03 (m, 1H), 1.99 – 1.91 (m, 1H)
¹³C NMR (CDCl₃, 125 MHz) δ 168.6, 161.5, 160.5, 143.8, 135.4, 134.8, 129.8, 128.9, 127.7, 124.0, 58.4, 48.2, 31.5, 24.7, 21.6
HRMS (ESI) m/z calcd. for C₂₀H₁₈N₂O₆S [M+H]⁺: 415.0958, found: 415.0952
Cyclic voltammetry conditions CHI620A; three-electrode configuration: glassy carbon working electrode, platinum wire counter electrode, Ag/AgNO₃ reference electrode (0.1 M AgNO₃ in MeCN); approximately 5 mM; MeCN, TBAPF₆ 0.25 M; N₂ sparge 5 min; 100 mV s⁻¹
Onset determination Irreversible event; onset potential determined graphically by extrapolating a tangent along the rising portion of the corresponding wave to the local background current
Potential reference Ferrocene internal standard; Fc/Fc⁺ midpoint assigned to 0.00 V; Fc/Fc⁺ observed at approximately +0.07 V vs. Ag/AgNO₃; potentials converted to the Fc/Fc⁺ scale by subtracting approximately 0.07 V; reported onset referenced to Fc/Fc⁺
Onset redox potential -1.37V vs. Ag/AgNO₃ → -1.44 V vs Fc/Fc⁺
SI, pp. S1-9, S1-58, S1-62
S(VI)-Pro-RAE derivative
Identifier S(VI)-Pro-RAE1
¹H NMR (CDCl₃, 500 MHz) δ 8.07 (d, J = 8.1 Hz, 2H), 7.89 (dd, J = 5.5, 3.1 Hz, 2H), 7.83 – 7.75 (m, 4H), 4.92 (t, J = 5.9 Hz, 1H), 3.56 (dt, J = 9.1, 7.6 Hz, 1H), 3.44 (ddd, J = 9.2, 7.6, 4.3 Hz, 1H), 2.39 (dt, J = 7.4, 5.5 Hz, 2H), 2.16 – 2.02 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 168.4, 161.5, 142.2, 134.9, 134.7, 134.4, 128.8, 128.1, 126.3, 126.3, 126.3, 126.2, 124.4, 124.1, 122.2, 58.4, 48.1, 31.6, 24.7
¹⁹F NMR (CDCl₃, 376 MHz) δ -63.1
HRMS (ESI) m/z calcd. for C₂₀H₁₅F₃N₂O₆S [M+H]⁺: 469.0676, found: 469.0671
SI, p. S1-10
S(VI)-Pro-RAE derivative
Identifier S(VI)-Pro-RAE2
¹H NMR (CDCl₃, 500 MHz) δ 7.93 – 7.85 (m, 4H), 7.83 – 7.76 (m, 2H), 7.01 – 6.95 (m, 2H), 4.80 (dd, J = 8.8, 3.3 Hz, 1H), 3.86 (s, 3H), 3.47 – 3.41 (m, 2H), 2.35 (ddt, J = 14.7, 7.6, 3.6 Hz, 1H), 2.28 (ddt, J = 16.1, 9.0, 4.4 Hz, 1H), 2.14 – 2.01 (m, 1H), 2.01 – 1.91 (m, 1H)
¹³C NMR (CDCl₃, 125 MHz) δ 168.7, 163.2, 161.5, 134.8, 130.0, 129.8, 128.9, 124.0, 114.3, 58.3, 55.6, 48.1, 31.6, 24.7
HRMS (ESI) m/z calcd. for C₂₀H₁₈N₂O₇S [M+H]⁺: 431.0908, found: 431.0902
SI, p. S1-10
S(VI)-Pro-RAE derivative
Identifier S(VI)-Pro-RAE3
¹H NMR (CDCl₃, 500 MHz) δ 7.99 – 7.94 (m, 2H), 7.89 (dd, J = 5.5, 3.0 Hz, 2H), 7.80 (dd, J = 5.4, 3.0 Hz, 2H), 7.18 (d, J = 8.8 Hz, 2H), 4.87 (dd, J = 7.9, 4.0 Hz, 1H), 3.54 – 3.48 (m, 1H), 3.43 (ddd, J = 9.1, 7.5, 4.0 Hz, 1H), 2.42 – 2.31 (m, 2H), 2.16 – 1.98 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 168.7, 166.5, 164.5, 161.6, 135.0, 134.9, 134.8, 130.6, 130.5, 129.0, 124.2, 116.6, 116.4, 58.5, 48.2, 31.7, 24.8
¹⁹F NMR (CDCl₃, 376 MHz) δ -105.0
HRMS (ESI) m/z calcd. for C₁₉H₁₅FN₂O₆S [M+H]⁺: 419.0708, found: 419.0701
SI, p. S1-10
S(VI)-Pro-RAE derivative
Identifier S(VI)-Pro-RAE4
¹H NMR (CDCl₃, 500 MHz) δ 9.13 (d, J = 2.2 Hz, 1H), 8.79 (dd, J = 4.7, 1.6 Hz, 1H), 8.23 (dt, J = 8.3, 1.8 Hz, 1H), 7.89 (dd, J = 5.5, 3.0 Hz, 2H), 7.80 (dd, J = 5.4, 3.0 Hz, 2H), 7.48 – 7.44 (m, 1H), 4.93 (t, J = 5.9 Hz, 1H), 3.58 (dt, J = 9.1, 7.6 Hz, 1H), 3.45 (ddd, J = 9.1, 7.4, 4.3 Hz, 1H), 2.40 (dt, J = 7.4, 5.8 Hz, 2H), 2.17 – 2.05 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 168.4, 161.4, 153.5, 148.3, 135.5, 135.4, 134.9, 128.8, 124.1, 123.8, 58.5, 48.0, 31.6, 24.7
HRMS (ESI) m/z calcd. for C₁₈H₁₅N₃O₆S [M+H]⁺: 402.0754 found: 402.0750
SI, p. S1-11
S(VI)-Pro-RAE derivative
Identifier S(VI)-Pro-RAE5
¹H NMR (CDCl₃, 500 MHz) δ 7.87 (dt, J = 7.3, 3.8 Hz, 2H), 7.79 (dd, J = 5.4, 3.1 Hz, 2H), 4.85 (dd, J = 8.4, 3.6 Hz, 1H), 3.68 – 3.61 (m, 1H), 3.52 (dt, J = 9.1, 5.9 Hz, 1H), 2.68 (s, 3H), 2.52 – 2.43 (m, 2H), 2.42 (s, 3H), 2.18 – 2.09 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 174.0, 168.4, 161.4, 157.9, 134.9, 128.8, 124.1, 115.7, 57.8, 48.5, 31.8, 24.6, 12.9, 11.0
HRMS (ESI) m/z calcd. for C₁₈H₁₇N₃O₇S [M+NH₄]⁺: 437.1126, found: 437.1124
SI, p. S1-11
S(VI)-Pro-RAE derivative
Identifier S(VI)-Pro-RAE6
¹H NMR (CDCl₃, 500 MHz) δ 7.91 – 7.86 (m, 2H), 7.81 (ddd, J = 5.5, 4.0, 2.4 Hz, 2H), 4.87 (dd, J = 8.6, 3.3 Hz, 1H), 3.70 – 3.62 (m, 1H), 3.58 (ddd, J = 8.9, 7.5, 4.5 Hz, 1H), 2.63 – 2.55 (m, 1H), 2.45 (m, 2H), 2.22 – 2.07 (m, 2H), 1.21 (dtt, J = 6.5, 4.8, 2.7 Hz, 2H), 1.07 – 0.98 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 169.5, 161.8, 135.1, 129.0, 124.2, 58.6, 48.4, 31.7, 30.0, 24.9, 5.6, 5.5
HRMS (ESI) m/z calcd. for C₁₆H₁₆N₂O₆S [M+NH₄]⁺: 382.1067, found: 382.0161
SI, pp. S1-11–S1-12
S(VI)-Pro-RAE derivative
Identifier Ms-Pro-RAE
¹H NMR (CDCl₃, 500 MHz) δ 7.90 (dd, J = 5.5, 3.1 Hz, 2H), 7.81 (dd, J = 5.5, 3.0 Hz, 2H), 4.93 (dd, J = 8.3, 3.6 Hz, 1H), 3.66 (m, 1H), 3.49 (ddd, J = 8.9, 7.0, 5.0 Hz, 1H), 3.05 (s, 3H), 2.52 – 2.39 (m, 2H), 2.22 – 2.10 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 169.2, 161.7, 135.1, 129.0, 124.3, 58.6, 48.0, 40.1, 31.5, 25.1
HRMS (ESI) m/z calcd. for C₁₄H₁₄N₂O₆S [M+NH₄]⁺: 356.0911, found: 356.0907
SI, p. S1-12
S(VI)-Pro-RAE derivative
Identifier FS-Pro-RAE
¹H NMR (CDCl₃, 500 MHz) δ 7.91 (dd, J = 5.5, 3.1 Hz, 2H), 7.82 (dd, J = 5.5, 3.1 Hz, 2H), 4.86 (td, J = 6.0, 1.8 Hz, 1H), 3.80 (dddt, J = 8.5, 7.0, 4.3, 2.2 Hz, 1H), 3.73 – 3.61 (m, 1H), 2.58 – 2.51 (m, 2H), 2.30 – 2.16 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 167.15, 161.34, 134.99, 128.81, 124.17, 59.74, 49.98, 31.50, 24.43
¹⁹F NMR (CDCl₃, 376 MHz) δ 44.49
HRMS (ESI) m/z calcd. for C₁₃H₁₁FN₂O₆S [M+NH₄]⁺: 360.0660, found: 360.0656
Cyclic voltammetry conditions CHI620A; three-electrode configuration: glassy carbon working electrode, platinum wire counter electrode, Ag/AgNO₃ reference electrode (0.1 M AgNO₃ in MeCN); approximately 5 mM; MeCN, TBAPF₆ 0.25 M; N₂ sparge 5 min; 100 mV s⁻¹
Onset determination Irreversible event; onset potential determined graphically by extrapolating a tangent along the rising portion of the corresponding wave to the local background current
Potential reference Ferrocene internal standard; Fc/Fc⁺ midpoint assigned to 0.00 V; Fc/Fc⁺ observed at approximately +0.07 V vs. Ag/AgNO₃; potentials converted to the Fc/Fc⁺ scale by subtracting approximately 0.07 V; reported onset referenced to Fc/Fc⁺
Onset redox potential -1.33V vs. Ag/AgNO₃ → -1.40 V vs Fc/Fc⁺
SI, pp. S1-13, S1-58, S1-62
Fluoroalkyl radical precursor
Identifier Tf-Pro-OBn
¹H NMR (CDCl₃, 500 MHz) δ 7.40 – 7.30 (m, 5H), 5.18 (s, 2H), 4.54 (d, J = 8.3 Hz, 1H), 3.78 – 3.70 (m, 1H), 3.67 – 3.58 (m, 1H), 2.37 – 2.19 (m, 1H), 2.17 – 1.96 (m, 3H)
¹³C NMR (CDCl₃, 125 MHz) δ 170.6, 135.1, 128.7, 128.6, 128.3, 120.1 (q, J = 323.2 Hz), 67.6, 61.5, 49.5, 31.1, 24.4
¹⁹F NMR (CDCl₃, 376 MHz) δ -78.51 (s, 3F)
SI, pp. S1-13–S1-14
Fluoroalkyl radical precursor
Identifier Tf-Pro-OH
¹H NMR (CDCl₃, 500 MHz) δ 11.11 (s, 1H), 4.53 (d, J = 5.9 Hz, 1H), 3.80 – 3.72 (m, 1H), 3.70 – 3.61 (m, 1H), 2.44 – 2.33 (m, 1H), 2.31 – 2.22 (m, 1H), 2.22 – 2.03 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 177.0, 120.1 (q, J = 323.1 Hz), 61.2, 49.6, 31.2, 24.4
¹⁹F NMR (CDCl₃, 376 MHz) δ -78.39 (s, 3F)
SI, p. S1-14
Fluoroalkyl radical precursor
Identifier Tf-Pro-RAE
¹H NMR (CDCl₃, 400 MHz) δ 7.93 – 7.85 (m, 2H), 7.85 – 7.77 (m, 2H), 4.92 (d, J = 5.6 Hz, 1H), 3.87 – 3.57 (m, 2H), 2.61 – 2.44 (m, 2H), 2.34 – 2.13 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 166.6, 160.3, 134.0, 127.7, 123.1, 118.9 (q, J = 322.9 Hz), 58.4, 48.6, 30.7, 23.3
¹⁹F NMR (CDCl₃, 470 MHz) δ -78.48 (s, 3F)
Cyclic voltammetry conditions CHI620A; three-electrode configuration: glassy carbon working electrode, platinum wire counter electrode, Ag/AgNO₃ reference electrode (0.1 M AgNO₃ in MeCN); approximately 5 mM; MeCN, TBAPF₆ 0.25 M; N₂ sparge 5 min; 100 mV s⁻¹
Onset determination Irreversible event; onset potential determined graphically by extrapolating a tangent along the rising portion of the corresponding wave to the local background current
Potential reference Ferrocene internal standard; Fc/Fc⁺ midpoint assigned to 0.00 V; Fc/Fc⁺ observed at approximately +0.07 V vs. Ag/AgNO₃; potentials converted to the Fc/Fc⁺ scale by subtracting approximately 0.07 V; reported onset referenced to Fc/Fc⁺
Onset redox potential -1.37V vs. Ag/AgNO₃ → -1.44 V vs Fc/Fc⁺
SI, pp. S1-14, S1-58, S1-62
Ms-Pro-OBn
Identifier S8
¹H NMR (CDCl₃, 500 MHz) δ 7.41 – 7.29 (m, 5H), 5.21 – 5.14 (ABq J = 12.2 Hz, 2H), 4.56 (dd, J = 8.6, 3.8 Hz, 1H), 3.60 – 3.51 (m, 1H), 3.43 (ddd, J = 9.5, 7.2, 5.3 Hz, 1H), 2.96 (s, 3H), 2.33 – 2.22 (m, 1H), 2.10 – 1.91 (m, 3H)
¹³C NMR (CDCl₃, 125 MHz) δ 172.3, 135.3, 128.7, 128.5, 128.2, 67.2, 60.6, 47.8, 39.4, 30.9, 24.9
HRMS (ESI) m/z calcd. for C₁₃H₂₇NO₄S [M+H]⁺ = 284.0951, found: 284.0950
SI, p. S1-15
Df-Pro-OH material
Identifier S9
¹H NMR (CDCl₃, 500 MHz) δ 3.80 – 3.72 (m, 1H), 3.67 (ddd, J = 11.2, 6.9, 4.1 Hz, 1H), 3.61 (dt, J = 11.3, 5.6 Hz, 1H), 3.45 (dt, J = 10.0, 6.2 Hz, 1H), 3.39 (dt, J = 10.2, 6.5 Hz, 1H), 2.87 (s, 3H), 2.56 (dd, J = 6.9, 5.3 Hz, 1H), 2.11 – 1.92 (m, 2H), 1.91 – 1.81 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 65.7, 61.9, 49.8, 34.9, 29.1, 24.7
HRMS (ESI) m/z calcd. for C₆H₁₃NO₃S [M+H]⁺ = 180.0689, found: 180.0687
SI, p. S1-16
Df-Pro-OH material
Identifier S10
¹H NMR (CDCl₃, 500 MHz) δ 7.40 – 7.26 (m, 5H), 4.54 (s, 2H), 3.98 – 3.79 (m, 1H), 3.63 (dd, J = 9.5, 4.2 Hz, 1H), 3.46 (dd, J = 9.5, 7.2 Hz, 1H), 3.41 – 3.36 (m, 1H), 3.36 – 3.29 (m, 1H), 2.82 (s, 3H), 2.03 – 1.83 (m, 4H)
¹³C NMR (CDCl₃, 125 MHz) δ 138.2, 128.5, 127.8, 127.8, 73.5, 72.7, 59.2, 49.1, 35.9, 29.2, 24.7
HRMS (ESI) m/z calcd. for C₁₃H₁₉NO₃S [M+H]⁺ = 270.1158, found: 270.1152
SI, p. S1-16
Df-Pro-OH material
Identifier S11
HRMS (ESI) m/z calcd for C₁₅H₁₈F₃NO₄S [M+H]⁺ 366.0981, found 366.0979
SI, p. S1-16
Df-Pro-OH material
Identifier S12
¹H NMR (CDCl₃, 500 MHz) δ 7.38 – 7.25 (m, 5H), 6.21 (t, J = 53.9 Hz, 1H), 4.54 – 4.50 (ABq, J = 11.8 Hz, 2H), 4.22 (dtd, J = 8.0, 5.3, 2.8 Hz, 1H), 3.66 (dt, J = 9.8, 6.8 Hz, 1H), 3.54 (dd, J = 9.8, 5.0 Hz, 1H), 3.51 – 3.36 (m, 2H), 2.14 – 1.86 (m, 4H)
¹³C NMR (CDCl₃, 125 MHz) δ 137.8, 128.5, 127.8, 127.7, 114.6 (t, J = 280.8 Hz), 73.3, 72.0, 59.8, 49.4, 28.8, 24.8
¹⁹F{¹H} NMR (CDCl₃, 376 MHz) δ -120.78 (d, J = 272.6 Hz, 1F), -122.00 (d, J = 272.8 Hz, 1F)
HRMS (ESI) m/z calcd. for C₁₃H₁₇F₂NO₃S [M+H]⁺ = 306.0970, found: 306.0961
SI, p. S1-17
Df-Pro-OH material
Identifier S13
¹H NMR (CDCl₃, 400 MHz) δ 6.34 (t, J = 53.8 Hz, 1H), 4.12 (dq, J = 8.8, 4.8 Hz, 1H), 3.72 (dq, J = 11.3, 5.4, 4.4 Hz, 2H), 3.61 (dd, J = 11.6, 5.5 Hz, 1H), 3.53 – 3.42 (m, 1H), 2.20 – 1.86 (m, 5H)
¹³C NMR (CDCl₃, 125 MHz) δ 114.9 (t, J = 280.9 Hz), 64.9, 62.5, 49.9, 28.7, 24.9
¹⁹F{¹H} NMR (CDCl₃, 376 MHz) δ -120.59 (d, J = 271.8 Hz, 1F), -121.43 (d, J = 272.3 Hz, 1F)
HRMS (ESI) m/z calcd. for C₆H₁₁F₂NO₃S [M+H]⁺ = 216.0501, found: 216.0499
SI, p. S1-17
Fluoroalkyl radical precursor
Identifier Df-Pro-OH
¹H{¹⁹F} NMR (CDCl₃, 400 MHz) δ 6.37 (s, 1H), 4.61 (dd, J = 8.7, 3.8 Hz, 1H), 3.75 – 3.59 (m, 2H), 2.48 – 2.34 (m, 1H), 2.28 – 2.16 (m, 1H), 2.13 – 2.01 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 176.5, 114.5 (t, J = 281.1 Hz), 60.9, 49.3, 30.9, 24.9
¹⁹F{¹H} NMR (CDCl₃, 376 MHz) δ -120.64 (d, J = 275.3 Hz, 1F), -121.86 (d, J = 275.2 Hz, 1F)
HRMS (ESI) m/z calcd. for C₆H₉F₂NO₄S [M−H]⁻ = 228.0148, found: 228.0142
SI, p. S1-17
Sulfonyl fluoride
Identifier 2a
¹H NMR (CDCl₃, 500 MHz) δ 7.29 (t, J = 7.5 Hz, 2H), 7.24 – 7.15 (m, 3H), 3.38 – 3.33 (m, 2H), 2.68 (t, J = 7.4 Hz, 2H), 2.03 – 1.93 (m, 2H), 1.82 (p, J = 7.5, 7.4 Hz, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 140.8, 128.7, 128.5, 126.4, 51.0, 50.8, 35.2, 29.6, 23.1
¹⁹F NMR (CDCl₃, 376 MHz) δ 53.6
HRMS (ESI) m/z calcd. for C₁₀H₁₃FO₂S [M+H]⁺ : 217.0693, found: 217.0694
SI, p. S1-26
Sulfonyl fluoride
Identifier 2b
¹H NMR (CDCl₃, 500 MHz) δ 7.37 – 7.30 (m, 2H), 7.16 (t, J = 7.7 Hz, 1H), 7.09 (d, J = 7.6 Hz, 1H), 3.37 (td, J = 7.6, 4.0 Hz, 2H), 2.65 (t, J = 7.5 Hz, 2H), 1.97 (h, J = 7.2, 7.0 Hz, 2H), 1.81 (p, J = 7.6, 7.4 Hz, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 143.0, 131.4, 130.2, 129.5, 127.0, 122.7, 50.7, 50.6, 34.7, 29.3, 23.0
¹⁹F NMR (CDCl₃, 376 MHz) δ 53.8
HRMS (ESI) m/z calcd. for C₁₀H₁₂BrFO₂S [M+Na]⁺ : 316.9618, found: 316.9613
SI, p. S1-27
Sulfonyl fluoride
Identifier 2c
¹H NMR (CDCl₃, 500 MHz) δ 8.50 – 8.44 (m, 2H), 7.50 (dt, J = 7.9, 1.9 Hz, 1H), 7.28 – 7.20 (m, 1H), 3.39 (td, J = 7.6, 4.1 Hz, 2H), 2.69 (t, J = 7.6 Hz, 2H), 2.05 – 1.95 (m, 2H), 1.84 (p, J = 7.7, 7.5 Hz, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 149.7, 147.8, 135.8, 123.5, 50.7, 50.6, 32.3, 29.2, 23.0
¹⁹F NMR (CDCl₃, 376 MHz) δ 53.9
HRMS (ESI) m/z calcd. for C₉H₁₂FNO₂S [M+H]⁺ : 218.0646, found: 218.0647
SI, p. S1-27
Sulfonyl fluoride
Identifier 2d
¹H NMR (CDCl₃, 500 MHz) δ 7.49 (d, J = 7.8 Hz, 2H), 7.32 (t, J = 7.6 Hz, 2H), 7.12 (t, J = 7.4 Hz, 1H), 3.41 (td, J = 7.7, 7.6, 4.1 Hz, 2H), 2.42 (t, J = 7.0 Hz, 2H), 2.09 – 1.99 (m, 2H), 1.91 (p, J = 7.2, 7.0 Hz, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 169.9, 137.7, 129.2, 124.7, 120.1, 50.8, 50.7, 36.4, 23.5, 23.2
¹⁹F NMR (CDCl₃, 376 MHz) δ 53.8
HRMS (ESI) m/z calcd. for C₁₀H₁₂BrFO₂S [M+H]⁺ : 260.0751, found: 260.0751
SI, p. S1-27
Sulfonyl fluoride
Identifier 2e
¹H NMR (CDCl₃, 500 MHz) δ 3.39 – 3.31 (m, 2H), 2.93 – 2.86 (m, 1H), 2.74 (td, J = 4.4, 3.8, 1.0 Hz, 1H), 2.48 – 2.43 (m, 1H), 1.94 (ddd, J = 15.3, 8.6, 6.9 Hz, 2H), 1.61 – 1.37 (m, 6H), 1.36 – 1.34 (m, 6H)
¹³C NMR (CDCl₃, 125 MHz) δ 52.4, 51.1, 50.9, 47.2, 32.5, 29.3, 29.2, 28.8, 27.9, 26.0, 23.5
¹⁹F NMR (CDCl₃, 376 MHz) δ 53.3
HRMS (ESI) m/z calcd. for C₁₀H₁₉FO₃S [M+H]⁺ : 239.1112, found: 239.1110
SI, p. S1-28
Sulfonyl fluoride
Identifier 2f
¹H NMR (CDCl₃, 500 MHz) δ 8.09 (d, J = 8.2 Hz, 2H), 7.37 – 7.31 (m, 2H), 7.08 – 7.02 (m, 2H), 3.39 (td, J = 7.5, 7.4, 3.8 Hz, 2H), 2.80 (t, J = 7.5 Hz, 2H), 2.06 – 1.95 (m, 2H), 1.88 (p, J = 7.6, 7.3 Hz, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 148.4, 134.5, 131.0, 129.1, 126.2, 123.8, 107.2, 107.2, 107.0, 107.0, 50.8, 50.7, 35.4, 29.2, 23.1
¹⁹F NMR (CDCl₃, 376 MHz) δ 54.0, -102.0
HRMS (ESI) m/z calcd. for C₁₈H₁₄F₃NO₄S [M+NH₄]⁺ : 415.0934, found: 435.0932
SI, p. S1-28
Sulfonyl fluoride
Identifier 2g
¹H NMR (CDCl₃, 500 MHz) δ 4.24 (t, J = 5.9 Hz, 2H), 4.05 (s, 2H), 3.50 – 3.43 (m, 2H), 2.82 (t, J = 12.5 Hz, 2H), 2.47 (tt, J = 11.2, 3.8 Hz, 1H), 2.34 – 2.25 (m, 2H), 1.88 (dd, J = 13.3, 3.8 Hz, 2H), 1.67 – 1.56 (m, 2H), 1.46 (s, 9H)
¹³C NMR (CDCl₃, 125 MHz) δ 174.3, 154.8, 79.9, 61.4, 48.1, 48.0, 41.2, 28.6, 28.1, 23.4
¹⁹F NMR (CDCl₃, 470 MHz) δ 53.9
HRMS (ESI) m/z calcd. for C₁₄H₂₄FNO₆S [M+Na]⁺ : 376.1201, found: 376.1198
SI, p. S1-28
Sulfonyl fluoride
Identifier 2h
¹H NMR (CDCl₃, 400 MHz) δ 7.59 (d, J = 7.9 Hz, 2H), 7.52 (d, J = 7.9 Hz, 2H), 7.31 (d, J = 7.9 Hz, 2H), 7.23 (d, J = 8.0 Hz, 2H), 3.95 (s, 1H), 3.81 – 3.73 (m, 1H), 3.62 – 3.54 (m, 1H), 3.50 (d, J = 11.7 Hz, 1H), 3.28 (td, J = 7.6, 4.0 Hz, 2H), 3.20 (td, J = 14.1, 13.0, 3.3 Hz, 1H), 2.45 (s, 3H), 2.39 (s, 3H), 2.28 (dd, J = 11.8, 3.5 Hz, 1H), 2.17 (td, J = 11.8, 3.3 Hz, 1H), 1.98 – 1.79 (m, J = 7.0 Hz, 2H), 1.76 – 1.56 (m, 2H), 1.41 (p, J = 7.8, 7.7 Hz, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 144.1, 143.9, 137.4, 132.4, 129.9, 129.8, 127.5, 127.0, 52.3, 50.6, 50.4, 48.0, 45.1, 40.0, 27.5, 24.3, 23.0, 21.6, 21.5
¹⁹F NMR (CDCl₃, 376 MHz) δ 53.7
HRMS (ESI) m/z calcd. for C₂₂H₂₉FN₂O₆S₃ [M+NH₄]⁺ : 550.1510, found: 550.1510
SI, p. S1-29
Sulfonyl fluoride
Identifier 2i
¹H NMR (CDCl₃, 500 MHz) δ 7.57 – 7.53 (m, 2H), 7.50 – 7.43 (m, 3H), 4.22 – 4.16 (m, 2H), 3.15 (tdd, J = 7.2, 3.9, 1.9 Hz, 2H), 2.75 (d, J = 1.1 Hz, 3H), 1.79 – 1.66 (m, 4H)
¹³C NMR (CDCl₃, 125 MHz) δ 176.6, 162.5, 162.0, 134.5, 129.9, 129.5, 128.9, 128.2, 123.7, 108.4, 63.4, 50.4, 50.3, 26.8, 20.5, 13.6
¹⁹F NMR (CDCl₃, 376 MHz) δ 53.9
HRMS (ESI) m/z calcd. for C₁₅H₁₆FNO₅S [M+H]⁺ : 342.0806, found: 342.0797
SI, p. S1-29
Sulfonyl fluoride
Identifier 2j
¹H NMR (CDCl₃, 500 MHz) δ 7.35 (m, 5H), 5.12 (s, 2H), 4.23 (s, 2H), 3.30 (dd, JH-H = 6.6, JH-F = 3.4 Hz, 2H), 2.84 (s, 2H), 2.24 (ttt, J = 10.7, 6.8, 3.6 Hz, 1H), 1.40 – 1.28 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 155.2, 136.7, 128.7, 128.3, 128.1, 67.4, 56.7, 56.6, 43.6, 32.2, 31.2
¹⁹F NMR (CDCl₃, 376 MHz) δ 59.5
HRMS (ESI) m/z calcd. for C₁₄H₁₈FNO₄S [M+H]⁺ : 316.1013, found: 316.1008
SI, p. S1-29
Sulfonyl fluoride
Identifier 2k
¹H NMR (CDCl₃, 500 MHz) δ 7.63 (d, J = 8.3 Hz, 2H), 7.33 (d, J = 7.9 Hz, 2H), 3.86 – 3.79 (m, 2H), 3.28 (dd, JH-H = 6.2, JH-F = 3.5 Hz, 2H), 2.44 (s, 3H), 2.30 (td, J = 12.1, 2.3 Hz, 2H), 2.01 – 1.96 (m, 3H), 1.59 – 1.49 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 144.0, 133.0, 129.9, 127.9, 56.3, 56.2, 45.8, 31.6, 30.8, 30.8, 21.7, 0.1
¹⁹F NMR (CDCl₃, 470 MHz) δ 59.2
HRMS (ESI) m/z calcd. for C₁₃H₁₈FNO₄S₂ [M+H]⁺ : 336.0734, found: 336.0730
SI, p. S1-30
Sulfonyl fluoride
Identifier 2l
¹H NMR (CDCl₃, 500 MHz) δ 4.20 (t, J = 8.6 Hz, 2H), 3.79 (dd, J = 9.1, 5.4 Hz, 2H), 3.66 (dd, J = 7.6, 4.2 Hz, 2H), 3.21 – 3.09 (m, 1H), 1.44 (s, 9H)
¹³C NMR (CDCl₃, 125 MHz) δ 156.1, 80.4, 54.3, 54.2, 28.5, 24.2
¹⁹F NMR (CDCl₃, 376 MHz) δ 55.6
HRMS (ESI) m/z calcd. for C₉H₁₆FNO₄S [M+H]⁺ : 254.0857, found: 254.0853
SI, p. S1-30
Sulfonyl fluoride
Identifier 2m
NMR observation Compound 2m was observed as a mixture of rotamers by NMR spectroscopy
¹H NMR (CDCl₃, 500 MHz) δ 3.81 – 3.67 (m, 1H), 3.58 – 3.29 (m, 4H), 3.11 (dd, J = 11.1, 8.1 Hz, 1H), 2.80 (s, 1H), 2.25 (s, 1H), 1.76 (s, 1H), 1.46 (s, 9H)
¹³C NMR (CDCl₃, 125 MHz) δ 154.3, 80.0, 53.8, 53.7, 50.5, 50.3, 45.2, 44.8, 34.2, 33.4, 31.2, 31.1, 30.7, 28.6
¹⁹F NMR (CDCl₃, 376 MHz) δ 56.7, 56.5
HRMS (ESI) m/z calcd. for C₁₀H₁₈FNO₄S [M+H]⁺ : 268.1013, found: 268.1008
SI, p. S1-30
Sulfonyl fluoride
Identifier 2n
¹H NMR (CDCl₃, 500 MHz) δ 4.07 (tt, J = 8.8, 5.8 Hz, 1H), 3.70 – 3.66 (m, 4H), 3.64 – 3.60 (m, 2H), 3.57 – 3.45 (m, 2H), 3.26 (p, J = 7.1 Hz, 1H), 2.60 (dt, J = 14.9, 7.6 Hz, 1H), 2.39 – 2.24 (m, 3H), 2.21 – 2.11 (m, 1H), 1.98 – 1.87 (m, 1H)
¹³C NMR (CDCl₃, 125 MHz) δ 171.0, 67.0, 66.8, 60.3, 60.2, 46.1, 42.6, 40.8, 31.5, 29.1, 27.8
¹⁹F NMR (CDCl₃, 470 MHz) δ 46.0
HRMS (ESI) m/z calcd. for C₁₀H₁₆FNO₄S [M+H]⁺ : 266.0857, found: 266.0856
SI, p. S1-31
Sulfonyl fluoride
Identifier 2o
¹H NMR (CDCl₃, 500 MHz) δ 7.37 – 7.29 (m, 5H), 5.13 (s, 2H), 3.96 (tt, J = 8.9, 6.0 Hz, 1H), 3.14 (app p, J = 7.0, 6.8 Hz, 1H), 2.57 – 2.48 (m, 1H), 2.46 – 2.39 (m, 1H), 2.34 – 2.19 (m, 3H), 2.05 – 1.94 (m, 1H)
¹³C NMR (CDCl₃, 125 MHz) δ 174.1, 135.7, 128.8, 128.7, 128.4, 67.0, 60.3, 60.2, 43.4, 31.3, 29.6, 27.7
¹⁹F NMR (CDCl₃, 470 MHz) δ 46.0
HRMS (ESI) m/z calcd. for C₁₃H₁₅FO₄S [M+NH₄]⁺ : 304.1013, found: 304.1013
SI, p. S1-31
Sulfonyl fluoride
Identifier 2p
¹H NMR (CDCl₃, 400 MHz) δ 8.00 (d, J = 8.8 Hz, 2H), 6.91 (d, J = 8.8 Hz, 2H), 4.46 – 4.42 (m, 2H), 3.98 (td, J = 5.9, 1.4 Hz, 2H), 3.85 (s, 3H), 3.82 – 3.80 (m, 2H), 3.69 (app s, 4H), 4.01 – 3.97 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 166.4, 163.6, 131.8, 122.6, 113.8, 71.2, 70.8, 69.6, 64.4, 63.8, 55.6, 51.4, 51.3
¹⁹F NMR (CDCl₃, 376 MHz) δ 58.9
HRMS (ESI) m/z calcd. for C₁₄H₁₉FO₇S [M+H]⁺ : 351.0908, found: 351.0905
SI, p. S1-31
Sulfonyl fluoride
Identifier 2q
¹H NMR (CDCl₃, 400 MHz) δ 3.34 – 3.24 (m, 2H), 1.23 – 1.14 (m, 2H), 0.96 (t, J = 7.9 Hz, 9H), 0.64 – 0.46 (m, 6H)
¹³C NMR (CDCl₃, 125 MHz) δ 48.1, 48.0, 7.3, 5.7, 3.0
¹⁹F NMR (CDCl₃, 376 MHz) δ 47.7
HRMS (ESI) m/z calcd. for C₈H₁₉FO₂SSi [M−H]⁻ : 225.0786, found: 225.0786
SI, p. S1-32
Sulfonyl fluoride
Identifier 2r
¹H NMR (CDCl₃, 500 MHz) δ 7.93 (d, J = 7.8 Hz, 2H), 7.24 (d, J = 8.5 Hz, 2H), 4.49 – 4.44 (m, 2H), 4.07 – 4.00 (m, 2H), 3.88 – 3.82 (m, 2H), 3.68 – 3.62 (m, 2H), 2.41 (s, 3H)
¹³C NMR (CDCl₃, 125 MHz) δ 166.7, 144.0, 129.9, 129.3, 127.3, 69.8, 64.2, 63.5, 51.4, 51.3, 21.8
¹⁹F NMR (CDCl₃, 376 MHz) δ 59.2
HRMS (ESI) m/z calcd. for C₁₂H₁₅FO₅S [M+H]⁺ : 291.0697, found: 291.0696
SI, p. S1-32
Sulfonyl fluoride
Identifier 2s
¹H NMR (CDCl₃, 500 MHz) δ 8.14 (d, J = 8.2 Hz, 2H), 7.88 (d, J = 8.3 Hz, 2H), 4.42 (t, J = 6.0 Hz, 2H), 3.47 (td, J = 7.8, 4.0 Hz, 2H), 3.10 (t, J = 7.7 Hz, 4H), 2.14 (app p, J = 7.9, 7.6 Hz, 2H), 2.06 – 1.97 (m, 2H), 1.61 – 1.49 (m, 4H), 0.87 (t, J = 7.3 Hz, 6H)
¹³C NMR (CDCl₃, 125 MHz) δ 165.3, 144.8, 133.2, 130.4, 127.3, 64.2, 50.6, 50.5, 50.1, 27.2, 22.1, 20.6, 11.3
¹⁹F NMR (CDCl₃, 376 MHz) δ 54.1
HRMS (ESI) m/z calcd. for C₁₇H₂₆FNO₆S₂ [M+H]⁺ : 424.1258, found: 424.1256
SI, p. S1-32
Sulfonyl fluoride
Identifier 2t
¹H NMR (CDCl₃, 500 MHz) δ 7.76 (d, J = 8.4 Hz, 2H), 7.50 (d, J = 8.3 Hz, 2H), 7.17 (d, J = 7.8 Hz, 2H), 7.10 (d, J = 7.8 Hz, 2H), 6.75 (s, 1H), 3.48 (td, J = 7.3, 3.9 Hz, 2H), 3.04 (t, J = 6.5 Hz, 2H), 2.72 (s, 3H), 2.38 (s, 3H), 2.07 (p, J = 7.5, 7.4 Hz, 2H), 1.78 (p, J = 6.7 Hz, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 145.5, 144.5, 144.2, 143.9, 142.8, 140.0, 136.7, 129.9, 128.8, 128.4, 125.8, 125.7, 106.5, 106.4, 50.1, 50.0, 48.9, 34.9, 25.4, 21.4, 20.4
¹⁹F NMR (CDCl₃, 376 MHz) δ 54.5, -62.5
HRMS (ESI) m/z calcd. for C₂₂H₂₃F₄N₃O₄S₂ [M+H]⁺ : 534.1139, found: 534.1137
SI, p. S1-33
Sulfonyl fluoride
Identifier 2u
¹H NMR (CDCl₃, 500 MHz) δ 8.18 (d, J = 2.3 Hz, 1H), 8.09 (dd, J = 8.7, 2.3 Hz, 1H), 7.01 (d, J = 8.8 Hz, 1H), 4.36 (t, J = 6.1 Hz, 2H), 3.90 (d, J = 6.4 Hz, 2H), 3.47 (td, J = 7.6, 4.0 Hz, 2H), 2.76 (s, 3H), 2.26 – 2.08 (m, 3H), 2.02 – 1.93 (m, 2H), 1.09 (d, J = 6.6 Hz, 6H)
¹³C NMR (CDCl₃, 125 MHz) δ 167.7, 162.8, 162.0, 162.0, 132.8, 132.3, 126.0, 121.2, 115.5, 112.8, 103.2, 75.9, 63.8, 50.6, 50.5, 28.3, 27.2, 20.7, 19.2, 17.7
¹⁹F NMR (CDCl₃, 376 MHz) δ 54.0
HRMS (ESI) m/z calcd. for C₂₀H₂₃FN₂O₅S₂ [M+H]⁺ : 455.1105, found: 455.1115
SI, p. S1-33
Sulfone
Identifier 3a
¹H NMR (CDCl₃, 500 MHz) δ 7.75 (d, J = 8.2 Hz, 2H), 7.34 (d, J = 7.9 Hz, 2H), 7.27 – 7.22 (m, 3H), 7.19 – 7.14 (m, 1H), 7.11 – 7.07 (m, 2H), 3.10 – 3.03 (m, 2H), 2.58 (t, J = 7.3 Hz, 2H), 2.45 (s, 3H), 1.79 – 1.63 (m, 4H)
¹³C NMR (CDCl₃, 125 MHz) δ 144.7, 141.4, 136.4, 130.0, 128.6, 128.5, 128.2, 126.2, 56.4, 35.4, 30.2, 22.5, 21.8
HRMS (ESI) m/z calcd. for C₁₇H₂₀O₂S [M+NH₄]⁺ : 306.1522, found: 306.1518
SI, p. S1-34
Sulfone
Identifier 3b
¹H NMR (CDCl₃, 500 MHz) δ 8.43 (d, J = 4.7 Hz, 1H), 8.38 (s, 1H), 7.76 (d, J = 7.8 Hz, 2H), 7.43 (d, J = 7.7 Hz, 1H), 7.35 (d, J = 7.9 Hz, 2H), 7.19 (dd, J = 7.8, 4.7 Hz, 1H), 3.11 – 3.05 (m, 2H), 2.59 (t, J = 7.4 Hz, 2H), 2.45 (s, 3H), 1.82 – 1.64 (m, 4H)
¹³C NMR (CDCl₃, 125 MHz) δ 149.8, 147.7, 144.9, 136.7, 136.3, 135.9, 130.1, 128.2, 123.5, 56.2, 32.6, 29.8, 22.5, 21.8
HRMS (ESI) m/z calcd. for C₁₆H₁₉NO₂S [M+H]⁺ : 290.1209, found: 290.1204
SI, pp. S1-34–S1-35
Sulfone
Identifier 3c
¹H NMR (CDCl₃, 500 MHz) δ 7.79 – 7.74 (m, 2H), 7.48 (d, J = 7.9 Hz, 2H), 7.32 (dd, J = 18.5, 7.9 Hz, 4H), 7.10 (t, J = 7.3 Hz, 1H), 3.11 (t, J = 6.9 Hz, 2H), 2.44 (s, 3H), 2.36 (t, J = 6.6 Hz, 2H), 1.88 – 1.79 (m, 4H)
¹³C NMR (CDCl₃, 125 MHz) δ 170.3, 144.9, 137.9, 136.3, 130.1, 129.2, 128.2, 124.5, 119.9, 56.1, 36.9, 24.2, 22.4, 21.8
HRMS (ESI) m/z calcd. for C₁₈H₂₁NO₃S [M+H]⁺ : 332.1315, found: 332.1312
SI, p. S1-35
Sulfone
Identifier 3d
¹H NMR (CDCl₃, 500 MHz) δ 7.81 – 7.75 (m, 2H), 7.35 (d, J = 7.9 Hz, 2H), 3.07 – 3.02 (m, 2H), 2.88 (tdd, J = 6.2, 4.4, 3.2 Hz, 1H), 2.73 (dd, J = 5.0, 3.9 Hz, 1H), 2.47 – 2.42 (m, 4H), 1.73 – 1.65 (m, 2H), 1.56 – 1.39 (m, 4H), 1.36 – 1.24 (m, 8H)
¹³C NMR (CDCl₃, 125 MHz) δ 144.7, 136.5, 130.0, 128.2, 56.5, 52.5, 47.2, 32.6, 29.4, 29.3, 29.0, 28.4, 26.0, 22.8, 21.8
HRMS (ESI) m/z calcd. for C₁₇H₂₆O₃S [M+H]⁺ : 311.1675, found: 311.1673
SI, p. S1-35
Sulfone
Identifier 3e
¹H NMR (CDCl₃, 500 MHz) δ 8.07 – 8.03 (m, 2H), 7.77 (d, J = 8.0 Hz, 2H), 7.36 (d, J = 7.9 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 7.07 – 7.03 (m, 2H), 3.08 (t, J = 7.2 Hz, 2H), 2.71 (t, J = 7.1 Hz, 2H), 2.46 (s, 3H), 1.77 (qd, J = 11.5, 9.1, 4.6 Hz, 4H)
¹³C NMR (CDCl₃, 125 MHz) δ 163.4, 149.1, 144.9, 136.4, 130.8, 130.1, 129.1, 128.2, 125.8, 108.9, 107.2, 107.2, 107.0, 107.0, 56.2, 35.6, 29.7, 22.4, 21.8
¹⁹F NMR (CDCl₃, 376 MHz) δ -102.0
HRMS (ESI) m/z calcd. for C₂₅H₂₁F₂NO₄S [M+NH₄]⁺ : 487.1498, found: 487.1497
SI, pp. S1-35–S1-36
Sulfone
Identifier 3f
¹H NMR (CDCl₃, 500 MHz) δ 9.88 (s, 1H), 7.81 (d, J = 8.6 Hz, 4H), 7.38 – 7.34 (m, 2H), 6.95 – 6.91 (m, 2H), 4.12 (t, J = 5.9 Hz, 2H), 3.30 (dd, J = 8.4, 6.7 Hz, 2H), 2.45 (s, 3H), 2.30 – 2.23 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 190.8, 163.4, 145.1, 136.3, 132.1, 130.5, 130.2, 128.2, 114.8, 66.0, 53.3, 23.0, 21.8
HRMS (ESI) m/z calcd. for C₁₇H₁₈O₄S [M+H]⁺ : 319.0999, found: 319.0998
SI, p. S1-36
Sulfone
Identifier 3g
¹H NMR (CDCl₃, 500 MHz) δ 7.77 (dd, J = 8.2, 1.6 Hz, 2H), 7.35 (d, J = 7.8 Hz, 2H), 3.75 (heptet, J = 6.0 Hz, 1H), 3.07 (t, J = 8.1 Hz, 2H), 2.45 (s, 3H), 1.79 – 1.65 (m, 2H), 1.54 – 1.36 (m, 4H), 1.18 – 1.12 (m, 3H)
¹³C NMR (CDCl₃, 125 MHz) δ 144.8, 136.4, 130.0, 128.2, 67.7, 56.5, 38.6, 24.6, 23.8, 22.9, 21.8
HRMS (ESI) m/z calcd. for C₁₃H₂₀O₃S [M+H]⁺ : 257.1206, found: 257.1201
SI, p. S1-36
Sulfone
Identifier 3h
¹H NMR (CDCl₃, 400 MHz) δ 7.78 (d, J = 8.2 Hz, 2H), 7.36 (dt, J = 7.8, 0.7 Hz, 2H), 4.01 (t, J = 6.6 Hz, 2H), 3.09 – 3.02 (m, 2H), 2.45 (s, 3H), 2.03 (s, 3H), 1.71 (tt, J = 7.9, 6.1 Hz, 2H), 1.58 (ddd, J = 14.4, 7.3, 5.0 Hz, 2H), 1.45 – 1.27 (m, 4H)
¹³C NMR (CDCl₃, 125 MHz) δ 171.3, 144.8, 136.4, 130.0, 128.2, 64.3, 56.4, 28.4, 28.1, 25.6, 22.8, 21.8, 21.1
HRMS (ESI) m/z calcd. for C₁₂H₂₂O₄S [M+H]⁺ : 299.1312, found: 299.1310
SI, p. S1-36
Sulfone
Identifier 3i
¹H NMR (CDCl₃, 500 MHz) δ 7.78 (d, J = 8.1 Hz, 2H), 7.39 – 7.28 (m, 7H), 5.10 (s, 2H), 4.13 (s, 2H), 2.98 (d, J = 6.2 Hz, 2H), 2.87 – 2.74 (m, 2H), 2.45 (s, 3H), 2.24 – 2.13 (m, 1H), 1.93 – 1.84 (m, 2H), 1.26 (qd, J = 12.0, 4.1 Hz, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 155.3, 144.9, 137.3, 136.9, 130.2, 128.6, 128.2, 128.0, 127.9, 67.3, 62.1, 43.8, 32.0, 31.3, 21.8
HRMS (ESI) m/z calcd. for C₂₁H₂₅NO₄S [M+H]⁺ : 388.1577, Found: 388.1570
SI, p. S1-37
Sulfone
Identifier 3j
¹H NMR (CDCl₃, 500 MHz) δ 7.78 – 7.74 (m, 2H), 7.34 (d, J = 7.8 Hz, 2H), 3.18 (d, J = 7.2 Hz, 2H), 2.69 (heptet, J = 7.8 Hz, 1H), 2.44 (s, 3H), 2.08 – 1.99 (m, 2H), 1.94 – 1.83 (m, 1H), 1.83 – 1.65 (m, 3H)
¹³C NMR (CDCl₃, 125 MHz) δ 144.7, 136.9, 130.0, 128.2, 62.4, 30.0, 28.5, 21.8, 19.3
HRMS (ESI) m/z calcd. for C₁₂H₁₆O₂S [M+H]⁺ : 225.0944, found: 225.0944
SI, p. S1-37
Sulfone
Identifier 3k
¹H NMR (CDCl₃, 500 MHz) δ 7.79 – 7.75 (m, 2H), 7.34 (d, J = 7.9 Hz, 2H), 3.50 – 3.41 (m, 1H), 2.05 (ddd, J = 14.1, 7.2, 7.1 Hz, 2H), 1.91 – 1.81 (m, 2H), 1.80 – 1.70 (m, 2H), 1.65 – 1.53 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 144.5, 136.2, 129.9, 128.6, 64.4, 27.4, 26.0, 21.7
HRMS (ESI) m/z calcd. for C₁₂H₁₆O₂S [M+NH₄]⁺ : 242.1209, found: 242.1205
SI, p. S1-37
Sulfone
Identifier 3l
¹H NMR (CDCl₃, 500 MHz) δ 7.74 (d, J = 6.7 Hz, 2H), 7.34 (d, J = 7.8 Hz, 2H), 3.09 (ddt, J = 12.1, 10.0, 4.6 Hz, 1H), 2.44 (s, 3H), 2.16 – 2.08 (m, 1H), 1.89 – 1.84 (m, 2H), 1.71 – 1.66 (m, 1H), 1.59 – 1.31 (m, 8H), 1.17 – 1.07 (m, 3H), 1.02 – 0.97 (m, 1H)
¹³C NMR (CDCl₃, 125 MHz) δ 144.5, 135.1, 129.8, 129.0, 58.4, 42.3, 42.3, 42.2, 41.5, 32.9, 29.6, 29.6, 23.6, 22.8, 21.8, 20.2
HRMS (ESI) m/z calcd. for C₁₈H₂₄O₂S [M+NH₄]⁺ : 322.1835, found: 322.1837
SI, p. S1-38
Sulfone
Identifier 3m
¹H NMR (CDCl₃, 500 MHz) δ 7.80 – 7.77 (m, 2H), 7.37 (d, J = 8.0 Hz, 2H), 3.64 (s, 3H), 3.43 – 3.37 (m, 2H), 2.77 – 2.72 (m, 2H), 2.45 (s, 3H)
¹³C NMR (CDCl₃, 125 MHz) δ 170.6, 145.2, 135.7, 130.2, 128.4, 52.4, 51.7, 27.9, 21.8
HRMS (ESI) m/z calcd. for C₁₁H₁₄O₄S [M+NH₄]⁺ : 260.0951, found: 260.0947
SI, p. S1-38
Sulfone
Identifier 3n
¹H NMR (CDCl₃, 500 MHz) δ 7.80 (d, J = 8.0 Hz, 2H), 7.41 (d, J = 8.0 Hz, 2H), 3.36 (t, J = 7.7 Hz, 2H), 2.82 – 2.77 (m, 2H), 2.48 (s, 3H)
¹³C NMR (CDCl₃, 125 MHz) δ 146.2, 134.7, 130.6, 128.5, 116.1, 51.4, 21.9, 12.2
HRMS (ESI) m/z calcd. for C₁₀H₁₁NO₂S [M+NH₄]⁺ : 227.0849, found: 227.0845
SI, p. S1-38
Sulfone
Identifier 3o
¹H NMR (CDCl₃, 500 MHz) δ 7.79 (d, J = 7.9 Hz, 2H), 7.33 (d, J = 7.9 Hz, 2H), 3.78 (t, J = 6.4, 2H), 3.37 (t, J = 6.4 Hz, 2H), 3.14 (tt, J = 8.1, 3.7 Hz, 1H), 2.44 (s, 3H), 1.71 (dt, J = 8.6, 3.6 Hz, 2H), 1.66 – 1.59 (m, 2H), 1.51 – 1.43 (m, 1H), 1.23 – 1.07 (m, 5H)
¹³C NMR (CDCl₃, 125 MHz) δ 144.7, 137.2, 129.8, 128.3, 78.1, 61.3, 57.0, 31.9, 25.8, 23.9, 21.8
HRMS (ESI) m/z calcd. for C₁₅H₂₂O₃S [M+NH₄]⁺ : 300.1628, found: 300.1629
SI, p. S1-39
Sulfone
Identifier 3p
¹H NMR (CDCl₃, 500 MHz) δ 7.81 – 7.75 (m, 2H), 7.36 (d, J = 7.9 Hz, 2H), 3.02 – 2.92 (m, 2H), 2.45 (s, 3H), 0.95 – 0.88 (m, 2H), 0.00 (s, 9H)
¹³C NMR (CDCl₃, 125 MHz) δ 144.6, 136.0, 130.0, 128.4, 53.0, 21.8, 9.4, -1.9
HRMS (ESI) m/z calcd. for C₁₂H₂₀O₂SSi [M+NH₄]⁺ : 274.1292, found: 274.1291
SI, p. S1-39
Sulfone
Identifier 3q
¹H NMR (CDCl₃, 500 MHz) δ 8.05 (d, J = 8.0 Hz, 2H), 7.85 (d, J = 8.1 Hz, 2H), 3.05 – 2.99 (m, 2H), 0.95 – 0.90 (m, 2H), 0.02 (s, 9H)
¹³C NMR (CDCl₃, 125 MHz) δ 142.5, 135.7, 135.4, 129.1, 126.6, 126.6, 126.5, 126.5, 124.4, 122.2, 53.0, 9.2, -1.9
¹⁹F NMR (CDCl₃, 376 MHz) δ -63.2
HRMS (ESI) m/z calcd. for C₁₂H₁₇F₃O₂SSi [M+H]⁺ : 311.0743, found: 311.0743
SI, p. S1-39
Sulfone
Identifier 3r
¹H NMR (CDCl₃, 500 MHz) δ 7.84 – 7.79 (m, 2H), 7.04 – 6.99 (m, 2H), 3.88 (s, 3H), 2.99 – 2.93 (m, 2H), 0.94 – 0.87 (m, 2H), -0.00 (s, 9H)
¹³C NMR (CDCl₃, 125 MHz) δ 163.8, 130.5, 130.5, 114.5, 55.8, 53.1, 9.5, -1.9
HRMS (ESI) m/z calcd. for C₁₂H₂₀O₃SSi [M+H]⁺ : 273.0975, found: 273.0975
SI, p. S1-40
Sulfone
Identifier 3s
¹H NMR (CDCl₃, 500 MHz) δ 7.94 – 7.88 (m, 2H), 7.26 – 7.21 (m, 2H), 3.01 – 2.94 (m, 2H), 0.94 – 0.87 (m, 2H), 0.00 (s, 9H)
¹³C NMR (CDCl₃, 125 MHz) δ 167.0, 164.9, 135.0, 134.9, 131.3, 131.2, 116.8, 116.6, 53.1, 9.4, -1.9
¹⁹F NMR (CDCl₃, 376 MHz) δ -103.8
HRMS (ESI) m/z calcd. for C₁₁H₁₇FO₂SSi [M+H]⁺ : 261.0775, found: 261.0774
SI, p. S1-40
Sulfone
Identifier 3t
¹H NMR (CDCl₃, 500 MHz) δ 9.14 – 9.08 (m, 1H), 8.88 (dd, J = 4.9, 1.6 Hz, 1H), 8.19 (dt, J = 8.0, 2.1 Hz, 1H), 7.56 – 7.50 (m, 1H), 3.07 – 2.99 (m, 2H), 0.97 – 0.89 (m, 2H), 0.02 (s, 9H)
¹³C NMR (CDCl₃, 125 MHz) δ 154.3, 149.5, 136.3, 135.4, 124.0, 53.4, 9.3, -1.9
HRMS (ESI) m/z calcd. for C₁₀H₁₇NO₂SSi [M+H]⁺ : 244.0822, found: 244.0823
SI, p. S1-40
Sulfone
Identifier 3u
¹H NMR (CDCl₃, 500 MHz) δ 2.99 – 2.94 (m, 2H), 2.66 (s, 3H), 2.43 (s, 3H), 0.94 – 0.89 (m, 2H), 0.05 (s, 9H)
¹³C NMR (CDCl₃, 125 MHz) δ 175.1, 158.2, 114.8, 53.8, 12.8, 11.1, 9.2, -1.9
HRMS (ESI) m/z calcd. for C₁₀H₁₉NO₃SSi [M+H]⁺ : 262.0928, found: 262.0927
SI, p. S1-41
Sulfone
Identifier 3v
¹H NMR (CDCl₃, 500 MHz) δ 2.97 – 2.91 (m, 2H), 2.41 – 2.33 (m, 1H), 1.27 – 1.20 (m, 2H), 1.11 – 1.05 (m, 2H), 1.05 – 1.00 (m, 2H), 0.08 – 0.05 (m, 9H)
¹³C NMR (CDCl₃, 125 MHz) δ 50.2, 28.4, 8.8, 4.6, -1.9
HRMS (ESI) m/z calcd. for C₈H₁₈O₂SSi [M+NH₄]⁺ : 224.1135, found: 224.1132
SI, p. S1-41
Sulfone
Identifier 3x
¹H NMR (CDCl₃, 500 MHz) δ 7.77 – 7.73 (m, 2H), 7.34 (d, J = 7.9 Hz, 2H), 6.69 (d, J = 7.7 Hz, 1H), 6.57 (d, J = 1.6 Hz, 1H), 6.53 (dd, J = 7.8, 1.8 Hz, 1H), 5.91 (s, 1H), 3.06 – 2.99 (m, 2H), 2.60 (t, J = 7.4 Hz, 2H), 2.45 (s, 3H), 1.98 (tt, J = 10.4, 6.7 Hz, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 147.9, 146.2, 144.8, 136.4, 133.8, 130.0, 128.2, 121.4, 108.9, 108.4, 101.0, 55.6, 34.0, 24.7, 21.8
HRMS (ESI) m/z calcd. for C₁₇H₁₈O₄S [M+NH₄]⁺ : 336.1264, found: 336.1258
SI, pp. S1-41–S1-42
Sulfone
Identifier 3y
¹H NMR (CDCl₃, 500 MHz) δ 7.78 – 7.73 (m, 2H), 7.67 – 7.62 (m, 2H), 7.50 – 7.44 (m, 2H), 7.35 (d, J = 7.9 Hz, 2H), 6.94 (d, J = 2.4 Hz, 1H), 6.85 (d, J = 9.0 Hz, 1H), 6.65 (dd, J = 9.0, 2.4 Hz, 1H), 4.05 (t, J = 6.4 Hz, 2H), 3.81 (s, 3H), 3.63 (s, 2H), 2.99 – 2.92 (m, 2H), 2.44 (s, 3H), 2.37 (s, 3H), 1.72 – 1.64 (m, 2H), 1.59 (p, J = 6.8 Hz, 2H), 1.35 (p, J = 6.6 Hz, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 170.9, 168.4, 156.2, 144.8, 139.5, 136.4, 136.1, 134.0, 131.3, 131.0, 130.8, 130.1, 129.3, 128.2, 115.1, 112.7, 111.6, 101.7, 64.5, 56.2, 55.9, 30.5, 28.3, 24.9, 22.5, 21.8, 13.5
HRMS (ESI) m/z calcd. for C₃₁H₃₂ClNO₆S [M+H]⁺ : 582.1712, found: 582.1713
SI, p. S1-42
Sulfone
Identifier 3z
¹H NMR (CDCl₃, 500 MHz) δ 7.81 – 7.76 (m, 2H), 7.75 – 7.71 (m, 2H), 7.50 – 7.44 (m, 2H), 7.40 – 7.33 (m, 2H), 7.17 (d, J = 7.8 Hz, 2H), 7.12 – 7.07 (m, 2H), 6.74 (s, 1H), 3.12 (t, J = 7.7 Hz, 2H), 2.96 (t, J = 6.8 Hz, 2H), 2.67 (s, 3H), 2.45 (s, 3H), 2.38 (s, 3H), 1.79 (p, J = 7.4 Hz, 2H), 1.68 (p, J = 7.0 Hz, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 145.3, 144.8, 142.6, 139.9, 136.8, 136.1, 130.0, 129.8, 128.7, 128.3, 128.1, 125.6, 125.6, 106.3, 106.3, 55.3, 49.2, 34.7, 26.0, 21.6, 21.3, 19.8
¹⁹F NMR (CDCl₃, 376 MHz) δ -62.5
HRMS (ESI) m/z calcd. for C₂₉H₃₀F₃N₃O₄S₂ [M+H]⁺ : 606.1703, found: 606.1702
SI, p. S1-42
Sulfone
Identifier 4b
NMR reporting reference ¹H and ¹³C chemical shifts: TMS (0.00 ppm); ¹⁹F chemical shifts: hexafluorobenzene (-164.9 ppm)
¹H NMR (CDCl₃, 500 MHz) δ 7.93 (d, J = 7.5 Hz, 2H), 7.72 (t, J = 7.3 Hz, 1H), 7.62 (t, J = 7.6 Hz, 2H), 3.32 – 3.23 (m, 2H), 2.63 – 2.50 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 138.2, 134.4, 129.7, 128.1, 125.4 (q, J = 276.4 Hz), 49.4 (q, J = 2.8 Hz), 28.1 (q, J = 31.5 Hz)
¹⁹F NMR (CDCl₃, 376 MHz) δ -69.1 (t, J = 9.9 Hz, 3F)
HRMS (ESI) m/z calcd. for C₉H₉F₃O₂S [M−H]⁻ = 237.0203, found: 237.0201. (0.8 ppm)
SI, pp. S1-43–S1-44
Ester
Identifier 4c
NMR reporting reference ¹H and ¹³C chemical shifts: TMS (0.00 ppm); ¹⁹F chemical shifts: hexafluorobenzene (-164.9 ppm)
¹H NMR (CDCl₃, 500 MHz) δ 7.34 – 7.27 (m, 2H), 7.27 – 7.23 (m, 1H), 7.23 – 7.18 (m, 2H), 4.33 (t, J = 7.0 Hz, 2H), 2.94 (t, J = 7.0 Hz, 2H), 2.59 – 2.52 (m, 2H), 2.42 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 170.9, 137.5, 128.9, 128.6, 126.7, 126.5 (q, J = 275.9 Hz), 65.5, 35.0, 29.3 (q, J = 30.1 Hz), 27.1 (q, J = 3.2 Hz)
¹⁹F NMR (CDCl₃, 376 MHz) δ -70.2 (t, J = 10.5 Hz, 3F)
ASAP-MS m/z calcd. for C₁₂H₁₃F₃O₂ [M+H]⁺ = 247.0940, found: 247.0936
SI, p. S1-44
Phenyl bromide
Identifier 4d
NMR reporting reference ¹H and ¹³C chemical shifts: TMS (0.00 ppm); ¹⁹F chemical shifts: hexafluorobenzene (-164.9 ppm)
¹H NMR (CDCl₃, 500 MHz) δ 7.35 – 7.30 (m, 2H), 7.15 (t, J = 7.8 Hz, 1H), 7.08 (d, J = 7.6 Hz, 1H), 2.60 (t, J = 7.5 Hz, 2H), 2.15 – 2.02 (m, 2H), 1.68 (p, J = 7.5 Hz, 2H), 1.59 (p, J = 7.7, 7.5 Hz, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 144.0, 131.4, 130.0, 129.1, 127.1 (q, J = 276.4 Hz), 127.0, 122.5, 35.2, 33.6 (q, J = 28.4 Hz), 30.2, 21.5 (q, J = 2.9 Hz)
¹⁹F NMR (CDCl₃, 376 MHz) δ -69.5 (t, J = 10.8 Hz, 3F)
ASAP-MS m/z calcd. for C₁₁H₁₂BrF₃ [M]⁺ = 280.0069, found: 280.0069
SI, p. S1-44
Pyridine
Identifier 4e
NMR reporting reference ¹H and ¹³C chemical shifts: TMS (0.00 ppm); ¹⁹F chemical shifts: hexafluorobenzene (-164.9 ppm)
¹H NMR (CDCl₃, 500 MHz) δ 8.38 (d, J = 4.8 Hz, 2H), 7.41 (dt, J = 7.8, 2.0 Hz, 1H), 7.15 (dd, J = 7.8, 4.7 Hz, 1H), 2.57 (t, J = 7.6 Hz, 2H), 2.10 – 1.97 (m, 2H), 1.64 (p, J = 7.5 Hz, 2H), 1.57 – 1.50 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 148.8, 146.6, 135.8, 134.7, 126.0 (q, J = 276.6 Hz), 122.4, 32.5 (q, J = 28.5 Hz), 31.6, 29.1, 20.5 (q, J = 3.0 Hz)
¹⁹F NMR (CDCl₃, 376 MHz) δ -69.5 (t, J = 10.8 Hz, 3F)
HRMS (ESI) m/z calcd. for C₁₀H₁₂F₃N [M+H]⁺ = 204.0995, found: 204.0995
SI, p. S1-44
Isoxazole
Identifier 4f
NMR reporting reference ¹H and ¹³C chemical shifts: TMS (0.00 ppm); ¹⁹F chemical shifts: hexafluorobenzene (-164.9 ppm)
¹H NMR (CDCl₃, 500 MHz) δ 7.56 (d, J = 8.0 Hz, 2H), 7.50 – 7.39 (m, 3H), 4.17 (t, J = 6.0 Hz, 2H), 2.74 (s, 3H), 2.03 – 1.89 (m, 2H), 1.61 (p, J = 6.6 Hz, 2H), 1.45 – 1.36 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 176.2, 162.5, 162.0, 129.7, 129.3, 128.7, 128.0, 126.9 (q, J = 276.3 Hz), 108.4, 65.0, 33.3 (q, J = 28.5 Hz), 27.5, 18.7 (q, J = 3.0 Hz), 13.5
¹⁹F NMR (CDCl₃, 376 MHz) δ -69.5 (t, J = 10.7 Hz, 3F)
HRMS (ESI) m/z calcd. for C₁₆H₁₆F₃NO₃ [M+H]⁺ = 328.1155, found: 328.1155
SI, p. S1-45
Styrene oxide
Identifier 4g
NMR reporting reference ¹H and ¹³C chemical shifts: TMS (0.00 ppm); ¹⁹F chemical shifts: hexafluorobenzene (-164.9 ppm)
¹H NMR (CDCl₃, 500 MHz) δ 8.02 – 7.97 (m, 2H), 7.40 – 7.31 (m, 2H), 4.38 (t, J = 6.2 Hz, 2H), 3.91 (dd, J = 4.1, 2.4 Hz, 1H), 3.19 (dd, J = 5.5, 4.0 Hz, 1H), 2.79 (dd, J = 5.5, 2.4 Hz, 1H), 2.33 – 2.18 (m, 2H), 2.10 – 1.99 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 166.0, 143.2, 129.8, 129.7, 126.9 (q, J = 276.1 Hz), 125.5, 63.2, 51.9, 51.5, 30.8 (q, J = 29.3 Hz), 21.7 (q, J = 3.1 Hz)
¹⁹F NMR (CDCl₃, 470 MHz) δ -69.5 (t, J = 10.7 Hz, 3F)
ASAP-MS m/z calcd. for C₁₃H₁₃F₃O₃ [M+H]⁺ = 275.0890, found: 275.0885
SI, p. S1-45
Aryl boronic ester
Identifier 4h
NMR reporting reference ¹H and ¹³C chemical shifts: TMS (0.00 ppm); ¹⁹F chemical shifts: hexafluorobenzene (-164.9 ppm); ¹¹B spectra: secondarily (Ξ) referenced to the appropriate ¹H spectrum
¹H NMR (CDCl₃, 500 MHz) δ 8.00 (d, J = 7.9 Hz, 2H), 7.87 (d, J = 7.8 Hz, 2H), 4.35 (t, J = 6.1 Hz, 2H), 2.16 (m, 2H), 1.86 (p, J = 6.8 Hz, 2H), 1.77 – 1.69 (m, 2H), 1.35 (s, 12H)
¹³C NMR (CDCl₃, 125 MHz) δ 166.6, 134.7, 132.3, 128.6, 127.0 (q, J = 276.2 Hz), 84.2, 64.2, 33.4 (q, J = 28.7 Hz), 27.8, 24.9, 18.8 (q, J = 3.0 Hz)
¹⁹F NMR (CDCl₃, 376 MHz) δ -69.6 (t, J = 11.1 Hz, 3F)
¹¹B NMR (161 MHz, CDCl₃) δ 30.2
ASAP-MS m/z calcd. for C₁₈H₂₄BF₃O₄ [M+H]⁺ = 373.1793, found: 373.1786
SI, p. S1-45
Benzoic acid
Identifier 4i
NMR reporting reference ¹H and ¹³C chemical shifts: TMS (0.00 ppm); ¹⁹F chemical shifts: hexafluorobenzene (-164.9 ppm)
¹H NMR (CDCl₃, 500 MHz) δ 7.73 (d, J = 7.6 Hz, 1H), 7.60 (s, 1H), 7.39 (t, J = 7.8 Hz, 1H), 7.15 (d, J = 7.9 Hz, 1H), 4.08 (t, J = 5.9 Hz, 2H), 2.40 – 2.27 (m, 2H), 2.12 – 2.02 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 171.5, 158.7, 130.6, 129.67, 127.1 (q, J = 276.0 Hz), 123.0, 120.8, 115.0, 66.3, 30.7 (q, J = 29.2 Hz), 22.2 (q, J = 3.1 Hz)
¹⁹F NMR (CDCl₃, 376 MHz) δ -69.5 (t, J = 10.8 Hz, 3F)
ASAP-MS m/z calcd. for C₁₁H₁₁F₃O₃ [M−H]⁻ = 247.0588, found: 247.0583
SI, pp. S1-45–S1-46
Azetidine
Identifier 4j
NMR reporting reference ¹H and ¹³C chemical shifts: TMS (0.00 ppm); ¹⁹F chemical shifts: hexafluorobenzene (-164.9 ppm)
¹H NMR (CDCl₃, 500 MHz) δ 4.10 (t, J = 8.5 Hz, 2H), 3.68 (dd, J = 8.6, 5.9 Hz, 2H), 2.90 – 2.78 (m, 1H), 2.39 (qd, J = 10.5, 7.3 Hz, 2H), 1.43 (s, 9H)
¹³C NMR (CDCl₃, 125 MHz) δ 156.1, 126.3 (q, J = 277.1 Hz), 79.7, 53.9, 37.9 (q, J = 28.4 Hz), 28.4, 23.0 (q, J = 3.2 Hz)
¹⁹F NMR (CDCl₃, 376 MHz) δ -69.1 (t, J = 10.5 Hz, 3F)
HRMS (ESI) m/z calcd. for C₁₀H₁₆F₃NO₂ [M+H]⁺ = 240.1206, found: 240.1205
SI, p. S1-46
Piperidine
Identifier 4k
NMR reporting reference ¹H and ¹³C chemical shifts: TMS (0.00 ppm); ¹⁹F chemical shifts: hexafluorobenzene (-164.9 ppm)
¹H NMR (CDCl₃, 500 MHz) δ 7.67 – 7.54 (m, 2H), 7.35 – 7.29 (m, 2H), 4.12 – 3.59 (m, 2H), 2.43 (s, 3H), 2.24 (td, J = 12.0, 2.5 Hz, 2H), 2.01 (qd, J = 11.2, 6.6 Hz, 2H), 1.83 (d, J = 12.8 Hz, 2H), 1.70 – 1.52 (m, 1H), 1.42 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 143.6, 133.0, 129.7, 127.7, 126.3 (q, J = 277.1 Hz), 46.0, 39.7 (q, J = 27.7 Hz), 31.3, 29.8 (q, J = 2.5 Hz), 21.5
¹⁹F NMR (CDCl₃, 376 MHz) δ -66.7 (t, J = 11.2 Hz, 3F)
HRMS (ESI) m/z calcd. for C₁₄H₁₈F₃NO₂S [M+H]⁺ = 322.1083, found: 322.1077
SI, p. S1-46
Piperidine
Identifier 4l
NMR reporting reference ¹H and ¹³C chemical shifts: TMS (0.00 ppm); ¹⁹F chemical shifts: hexafluorobenzene (-164.9 ppm)
¹H NMR (CDCl₃, 500 MHz) δ 7.39 – 7.27 (m, 5H), 5.12 (s, 2H), 4.18 (br s, 2H), 2.80 (br s, 2H), 2.02 (qd, J = 11.3, 6.5 Hz, 2H), 1.91 – 1.80 (m, 1H), 1.78 (d, J = 13.4 Hz, 2H), 1.32 – 1.17 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 155.2, 136.8, 128.5, 128.0, 127.9, 126.8 (q, J = 277.2 Hz), 67.1, 43.8, 40.0 (q, J = 27.5 Hz), 31.8, 30.5 (q, J = 2.4 Hz)
¹⁹F NMR (CDCl₃, 376 MHz) δ -66.5 (t, J = 11.2 Hz, 3F)
HRMS (ESI) m/z calcd. for C₁₅H₁₈F₃NO₂ [M+H]⁺ = 302.1362, found: 302.1361
SI, p. S1-46
Hydrotri(di)fluoromethylated material
Identifier 4m
NMR reporting reference ¹H and ¹³C chemical shifts: TMS (0.00 ppm); ¹⁹F chemical shifts: hexafluorobenzene (-164.9 ppm)
¹H NMR (CDCl₃, 400 MHz) δ 7.93 (d, J = 8.0 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 2.84 – 2.64 (m, 2H), 2.45 (s, 3H), 2.14 – 1.82 (m, 4H), 1.82 – 1.56 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 172.5, 145.4, 135.3, 129.7, 128.32, 127.9 (q, J = 277.4 Hz), 44.9, 42.3 (q, J = 27.7 Hz), 29.7, 28.9 (q, J = 2.5 Hz), 25.9 (q, J = 2.3 Hz), 21.7
¹⁹F NMR (CDCl₃, 376 MHz) δ -74.8 (d, J = 9.6 Hz, 3F)
HRMS (ESI) m/z calcd. for C₁₄H₁₆F₃NO₃S [M−H]⁻ = 334.0730, found: 334.0731. (0.3 ppm)
SI, pp. S1-46–S1-47
Anisole
Identifier 4n
NMR reporting reference ¹H and ¹³C chemical shifts: TMS (0.00 ppm); ¹⁹F chemical shifts: hexafluorobenzene (-164.9 ppm)
¹H NMR (CDCl₃, 500 MHz) δ 7.12 (d, J = 8.6 Hz, 2H), 6.84 (d, J = 8.4 Hz, 2H), 4.26 (t, J = 6.9 Hz, 2H), 3.78 (s, 3H), 3.08 – 2.75 (m, 3H), 2.80 – 2.64 (m, 1H), 2.18 – 1.88 (m, 4H), 1.86 – 1.64 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 175.1, 158.4, 129.8, 129.7, 128.2 (q, J = 277.0 Hz), 113.9, 65.3, 55.3, 43.5, 42.3 (q, J = 27.5 Hz), 34.2, 29.8, 29.4 (q, J = 2.4 Hz), 25.8 (q, J = 2.3 Hz)
¹⁹F NMR (CDCl₃, 376 MHz) δ -74.7 (d, J = 9.6 Hz, 3F)
ASAP-MS m/z calcd. for C₁₆H₁₉F₃O₃ [M+H]⁺ = 317.1359, found: 317.1359
SI, p. S1-47
Safrole derivative
Identifier 4o
NMR reporting reference ¹H and ¹³C chemical shifts: TMS (0.00 ppm); ¹⁹F chemical shifts: hexafluorobenzene (-164.9 ppm)
¹H NMR (CDCl₃, 500 MHz) δ 6.66 (d, J = 7.9 Hz, 1H), 6.58 (d, J = 1.2 Hz, 1H), 6.54 (dd, J = 7.9, 1.3 Hz, 1H), 5.85 (s, 2H), 2.53 (t, J = 7.5 Hz, 2H), 2.08 – 1.90 (m, 2H), 1.77 (p, J = 7.7 Hz, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 146.7, 145.0, 133.4, 126.2 (q, J = 276.6 Hz), 120.2, 107.7, 107.2, 99.9, 33.3, 31.9 (q, J = 28.5 Hz), 22.7 (q, J = 2.8 Hz)
¹⁹F NMR (CDCl₃, 470 MHz) δ -69.3 (t, J = 10.8 Hz, 3F)
ASAP-MS m/z calcd. for C₁₁H₁₁F₃O₂ [M+H]⁺ = 233.0784, found: 233.0780
SI, p. S1-47
Probenecid derivative
Identifier 4p
NMR reporting reference ¹H and ¹³C chemical shifts: TMS (0.00 ppm); ¹⁹F chemical shifts: hexafluorobenzene (-164.9 ppm)
¹H NMR (CDCl₃, 500 MHz) δ 8.18 – 8.10 (m, 2H), 7.91 – 7.84 (m, 2H), 4.38 (t, J = 6.3 Hz, 2H), 3.13 – 3.06 (m, 4H), 2.24 – 2.11 (m, 2H), 1.96 – 1.82 (m, 2H), 1.80 – 1.69 (m, 2H), 1.55 (h, J = 7.4 Hz, 4H), 0.87 (t, J = 7.4 Hz, 6H)
¹³C NMR (CDCl₃, 125 MHz) δ 165.2, 144.4, 133.4, 130.2, 127.1, 127.0 (q, J = 276.2 Hz), 64.8, 50.0, 33.4 (q, J = 28.7 Hz), 27.8, 22.0, 18.8 (q, J = 3.0 Hz), 11.2
¹⁹F NMR (CDCl₃, 470 MHz) δ -69.5 (t, J = 10.8 Hz, 3F)
ASAP-MS m/z calcd. for C₁₈H₂₆F₃NO₄S [M+H]⁺ = 410.1607, found: 410.1607
SI, p. S1-47
Indomethacin derivative
Identifier 4q
NMR reporting reference ¹H and ¹³C chemical shifts: TMS (0.00 ppm); ¹⁹F chemical shifts: hexafluorobenzene (-164.9 ppm)
¹H NMR (CDCl₃, 500 MHz) δ 7.65 (d, J = 7.8 Hz, 2H), 7.46 (d, J = 8.0 Hz, 2H), 6.96 (d, J = 1.6 Hz, 1H), 6.86 (d, J = 9.2 Hz, 1H), 6.70 – 6.63 (m, 1H), 4.10 (t, J = 6.4 Hz, 2H), 3.82 (s, 3H), 3.65 (s, 2H), 2.39 (s, 3H), 2.08 – 1.91 (m, 2H), 1.63 (p, J = 6.8 Hz, 2H), 1.52 (p, J = 7.9 Hz, 2H), 1.35 (p, J = 7.8, 7.5 Hz, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 170.9, 168.3, 156.1, 139.3, 136.0, 133.9, 131.2, 130.9, 130.7, 129.1, 127.1 (q, J = 276.3 Hz), 114.9, 112.6, 111.4, 101.6, 64.6, 55.7, 33.5 (q, J = 28.4 Hz), 30.4, 28.3, 25.1, 21.5 (q, J = 3.0 Hz), 13.3
¹⁹F NMR (CDCl₃, 376 MHz) δ -69.6 (t, J = 10.9 Hz, 3F)
HRMS (ESI) m/z calcd. for C₂₅H₂₅ClF₃NO₄ [M+H]⁺ = 496.1497, found: 496.1496
SI, p. S1-48
Febuxostat derivative
Identifier 4r
NMR reporting reference ¹H and ¹³C chemical shifts: TMS (0.00 ppm); ¹⁹F chemical shifts: hexafluorobenzene (-164.9 ppm)
¹H NMR (CDCl₃, 500 MHz) δ 8.18 (d, J = 2.2 Hz, 1H), 8.09 (dd, J = 8.8, 2.3 Hz, 1H), 7.01 (d, J = 8.7 Hz, 1H), 4.32 (t, J = 6.2 Hz, 2H), 3.90 (d, J = 6.3 Hz, 2H), 2.76 (s, 3H), 2.26 – 2.09 (m, 3H), 1.85 (p, J = 6.5 Hz, 2H), 1.77 – 1.67 (m, 2H), 1.09 (d, J = 6.5 Hz, 6H)
¹³C NMR (CDCl₃, 125 MHz) δ 167.4, 162.6, 162.0, 161.5, 132.6, 132.2, 127.0 (q, J = 276.3 Hz), 126.0, 121.5, 115.4, 112.7, 103.1, 75.7, 64.5, 33.4 (q, J = 28.7 Hz), 28.2, 27.8, 19.1, 18.8 (q, J = 3.3 Hz), 17.5
¹⁹F NMR (CDCl₃, 376 MHz) δ -69.5 (t, J = 10.8 Hz, 3F)
HRMS (ESI) m/z calcd. for C₂₁H₂₃F₃N₂O₃S [M+H]⁺ = 441.1454, found: 441.1454
SI, p. S1-48
Ester
Identifier 5a
NMR reporting reference ¹H and ¹³C chemical shifts: TMS (0.00 ppm); ¹⁹F spectra: secondarily (Ξ) referenced to the appropriate ¹H spectrum
¹H NMR (CDCl₃, 500 MHz) δ 7.27 – 7.20 (m, 2H), 7.20 – 7.11 (m, 3H), 5.79 (tt, J = 56.6, 4.2 Hz, 1H), 4.25 (t, J = 7.0 Hz, 2H), 2.87 (t, J = 7.0 Hz, 2H), 2.40 (t, J = 7.4 Hz, 2H), 2.05 (ttd, J = 17.3, 7.4, 4.2 Hz, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 172.0, 137.7, 129.0, 128.7, 126.8, 116.2 (t, J = 239.0 Hz), 65.4, 35.2, 29.4 (t, J = 22.3 Hz), 27.0 (t, J = 6.1 Hz)
¹⁹F{¹H} NMR (CDCl₃, 470 MHz) δ -117.6 (s, 2F)
HRMS (ESI) m/z calcd. for C₁₂H₁₄F₂O₂ [M+NH₄]⁺ = 246.1300, found: 246.1300
SI, p. S1-49
Phenyl bromide
Identifier 5b
NMR reporting reference ¹H and ¹³C chemical shifts: TMS (0.00 ppm); ¹⁹F spectra: secondarily (Ξ) referenced to the appropriate ¹H spectrum
¹H NMR (CDCl₃, 500 MHz) δ 7.34 – 7.27 (m, 2H), 7.17 – 7.04 (m, 2H), 5.79 (tt, J = 56.8, 4.4 Hz, 1H), 2.60 (t, J = 7.6 Hz, 2H), 1.94 – 1.76 (m, 2H), 1.66 (p, J = 7.7 Hz, 2H), 1.53 – 1.43 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 144.3, 131.4, 129.9, 129.0, 127.0, 122.5, 117.2 (t, J = 238.8 Hz), 35.3, 33.9 (t, J = 20.8 Hz), 30.6, 21.7 (t, J = 5.4 Hz)
¹⁹F{¹H} NMR (CDCl₃, 470 MHz) δ -115.8 (s, 2F)
HRMS (ESI) m/z calcd. for C₁₁H₁₃BrF₂ [M+H]⁺ = 263.0242, found: 263.0242
SI, pp. S1-49–S1-50
Naphthalene
Identifier 5c
NMR reporting reference ¹H and ¹³C chemical shifts: TMS (0.00 ppm); ¹⁹F spectra: secondarily (Ξ) referenced to the appropriate ¹H spectrum
¹H NMR (CDCl₃, 400 MHz) δ 7.83 – 7.74 (m, 3H), 7.60 (s, 1H), 7.49 – 7.37 (m, 2H), 7.31 (dd, J = 8.4, 1.7 Hz, 1H), 5.79 (tt, J = 56.8, 4.4 Hz, 1H), 2.80 (t, J = 7.6 Hz, 2H), 1.94 – 1.70 (m, 4H), 1.59 – 1.46 (m, 2H)
¹³C NMR (CDCl₃, 100 MHz) δ 139.4, 133.6, 132.0, 127.9, 127.6, 127.4, 127.2, 126.4, 125.9, 125.2, 117.3 (t, J = 238.9 Hz), 35.8, 34.0 (t, J = 20.9 Hz), 29.7, 21.8 (t, J = 5.7 Hz)
¹⁹F{¹H} NMR (CDCl₃, 376 MHz) δ -115.7 (s, 2F)
HRMS (ESI) m/z calcd. for C₁₅H₁₆F₂ [M+H]⁺ = 235.1293, found: 235.1292
SI, p. S1-50
Piperidine
Identifier 5d
NMR reporting reference ¹H and ¹³C chemical shifts: TMS (0.00 ppm); ¹⁹F spectra: secondarily (Ξ) referenced to the appropriate ¹H spectrum
¹H NMR (CDCl₃, 500 MHz) δ 7.56 (d, J = 8.1 Hz, 2H), 7.25 (d, J = 7.9 Hz, 2H), 5.75 (tt, J = 56.4, 4.5 Hz, 1H), 3.69 (dt, J = 11.1, 2.3 Hz, 2H), 2.36 (s, 3H), 2.17 (td, J = 11.8, 2.5 Hz, 2H), 1.77 – 1.60 (m, 4H), 1.49 – 1.38 (m, 1H), 1.33 (qd, J = 12.0, 11.8, 3.9 Hz, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 143.7, 133.2, 129.8, 127.9, 116.3 (t, J = 239.2 Hz), 46.2, 40.2 (t, J = 20.5 Hz), 31.6, 30.0 (t, J = 5.0 Hz), 21.7
¹⁹F{¹H} NMR (CDCl₃, 376 MHz) δ -115.2 (s, 2F)
HRMS (ESI) m/z calcd. for C₁₄H₁₉F₂NO₂S [M+H]⁺ = 304.1177, found: 304.1176
SI, p. S1-50
Probenecid derivative
Identifier 5e
NMR reporting reference ¹H and ¹³C chemical shifts: TMS (0.00 ppm); ¹⁹F spectra: secondarily (Ξ) referenced to the appropriate ¹H spectrum
¹H NMR (CDCl₃, 500 MHz) δ 8.14 (d, J = 8.4 Hz, 2H), 7.96 – 7.82 (m, 2H), 5.84 (tt, J = 56.5, 4.2 Hz, 1H), 4.37 (t, J = 6.4 Hz, 2H), 3.10 (dd, J = 8.6, 6.6 Hz, 4H), 2.09 – 1.73 (m, 4H), 1.70 – 1.60 (m, 2H), 1.55 (h, J = 7.4 Hz, 4H), 0.87 (t, J = 7.3 Hz, 6H)
¹³C NMR (CDCl₃, 125 MHz) δ 165.2, 144.4, 133.5, 130.2, 127.1, 117.0 (t, J = 239.0 Hz), 65.1, 49.9, 33.6 (t, J = 21.0 Hz), 28.2, 22.0, 18.8 (t, J = 5.5 Hz), 11.2
¹⁹F{¹H} NMR (CDCl₃, 376 MHz) δ -116.1 (s, 2F)
HRMS (ESI) m/z calcd. for C₁₈H₂₇F₂NO₄S [M+H]⁺ = 392.1702, found: 392.1699
SI, p. S1-50
Estrone-derived material
Identifier 6
¹H NMR (CDCl₃, 500 MHz) δ 7.29 (t, J = 7.6 Hz, 3H), 7.23 – 7.14 (m, 3H), 6.99 – 6.94 (m, 2H), 3.25 – 3.20 (m, 2H), 2.91 (dd, J = 9.0, 4.3 Hz, 2H), 2.68 (t, J = 7.5 Hz, 2H), 2.51 (dd, J = 18.9, 8.6 Hz, 1H), 2.39 (dt, J = 12.9, 3.6 Hz, 1H), 2.28 (td, J = 11.0, 4.2 Hz, 1H), 2.19 – 2.10 (m, 1H), 2.10 – 1.91 (m, 5H), 1.81 (p, J = 7.6 Hz, 2H), 1.68 – 1.39 (m, 8H), 0.91 (s, 3H)
¹³C NMR (CDCl₃, 125 MHz) δ 220.7, 147.1, 141.2, 139.1, 138.9, 128.7, 128.5, 127.0, 126.3, 122.2, 119.2, 50.6, 50.4, 48.0, 44.3, 38.1, 36.0, 35.4, 31.7, 30.0, 29.5, 26.4, 25.9, 23.2, 21.7, 14.0
HRMS (ESI) m/z calcd. for C₂₈H₃₄O₄S [M+H]⁺ : 467.2251, found: 467.2248
SI, p. S1-51
Sulfone
Identifier 7
¹H NMR (CDCl₃, 500 MHz) δ 7.77 (d, J = 1.8 Hz, 1H), 7.30 (dd, J = 7.7, 1.9 Hz, 1H), 7.27 – 7.22 (m, 2H), 7.21 – 7.14 (m, 2H), 7.11 – 7.08 (m, 2H), 3.14 – 3.07 (m, 2H), 2.60 (d, J = 12.5 Hz, 5H), 2.37 (s, 3H), 1.81 – 1.65 (m, 4H)
¹³C NMR (CDCl₃, 125 MHz) δ 141.4, 137.1, 136.7, 134.8, 134.5, 132.8, 130.6, 128.6, 128.4, 126.2, 55.4, 35.5, 30.2, 22.2, 21.0, 20.1
HRMS (ESI) m/z calcd. for C₁₈H₂₂O₂S [M+H]⁺ : 303.1413, found: 303.1409
SI, p. S1-51
Desloratadine-derived material
Identifier 8
¹H NMR (CDCl₃, 500 MHz) δ 8.40 (dd, J = 4.8, 1.6 Hz, 1H), 7.44 (dd, J = 7.7, 1.6 Hz, 1H), 7.28 (dd, J = 8.4, 6.8 Hz, 2H), 7.21 – 7.13 (m, 5H), 7.13 – 7.07 (m, 2H), 3.54 – 3.40 (m, 2H), 3.41 – 3.28 (m, 2H), 3.16 – 3.07 (m, 2H), 2.95 – 2.75 (m, 4H), 2.67 – 2.56 (m, 3H), 2.47 (ddd, J = 13.1, 8.4, 4.2 Hz, 1H), 2.37 (ddt, J = 13.7, 6.6, 3.5 Hz, 2H), 1.90 – 1.80 (m, 2H), 1.74 (p, J = 7.5 Hz, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 156.8, 146.9, 141.5, 139.7, 137.8, 137.6, 136.2, 135.2, 133.5, 133.3, 130.5, 129.2, 128.6, 128.5, 126.4, 126.2, 122.6, 49.7, 47.2, 35.5, 31.8, 31.7, 31.0, 30.8, 30.4, 22.9
HRMS (ESI) m/z calcd. for C₂₉H₃₁ClN₂O₂S [M+H]⁺ : 507.1868, found: 507.1868
SI, p. S1-52
Sulfonyl azide
Identifier 9
¹H NMR (CDCl₃, 500 MHz) δ 7.29 (t, J = 7.6 Hz, 2H), 7.23 – 7.18 (m, 1H), 7.18 – 7.14 (m, 2H), 3.34 – 3.27 (m, 2H), 2.67 (t, J = 7.5 Hz, 2H), 1.99 – 1.90 (m, 2H), 1.80 (p, J = 7.4, 7.1 Hz, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 141.0, 128.7, 128.5, 126.4, 55.9, 35.3, 29.8, 23.1
HRMS (ESI) m/z calcd. for C₁₀H₁₃N₃O₂S [M+NH₄]⁺ : 257.1067, found: 257.1066
SI, p. S1-52
Aziridine
Identifier 10
¹H NMR (CDCl₃, 500 MHz) δ 7.31 – 7.24 (m, 2H), 7.21 – 7.15 (m, 3H), 3.14 – 3.08 (m, 2H), 2.95 – 2.90 (m, 2H), 2.67 (t, J = 7.4 Hz, 2H), 1.92 (tt, J = 7.9, 6.1 Hz, 2H), 1.86 – 1.75 (m, 6H), 1.45 – 1.36 (m, 2H), 1.25 (tdd, J = 13.9, 7.7, 3.4 Hz, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 141.5, 128.6, 128.5, 126.2, 52.7, 39.3, 35.4, 30.1, 23.1, 22.9, 19.6
HRMS (ESI) m/z calcd. for C₁₆H₂₃NO₂S [M+H]⁺ : 294.1522, found: 294.1517
SI, p. S1-53
Sulfonyl triazole
Identifier 11
¹H NMR (CDCl₃, 500 MHz) δ 8.23 (s, 1H), 7.89 – 7.84 (m, 2H), 7.51 – 7.45 (m, 2H), 7.44 – 7.39 (m, 1H), 7.24 (d, J = 7.7 Hz, 2H), 7.18 – 7.14 (m, 1H), 7.12 – 7.08 (m, 2H), 3.69 – 3.61 (m, 2H), 2.62 (t, J = 7.3 Hz, 2H), 1.87 – 1.70 (m, 4H)
¹³C NMR (CDCl₃, 125 MHz) δ 147.5, 140.7, 129.4, 129.2, 128.8, 128.7, 128.4, 126.4, 126.3, 119.6, 55.3, 35.1, 29.5, 22.6
HRMS (ESI) m/z calcd. for C₁₈H₁₉N₃O₂S [M+H]⁺ : 342.1271, found: 342.1268
SI, p. S1-53
Sultam
Identifier 13
¹H NMR (CDCl₃, 500 MHz) δ 3.75 (dddd, J = 13.4, 8.5, 4.8, 2.3 Hz, 1H), 3.53 (dt, J = 11.5, 2.3 Hz, 1H), 3.18 – 3.07 (m, 3H), 2.87 (ddd, J = 11.5, 2.9, 1.9 Hz, 1H), 2.62 (dd, J = 11.8, 2.9 Hz, 1H), 1.91 – 1.82 (m, 1H), 1.59 (dtd, J = 10.1, 5.5, 2.6 Hz, 1H)
¹³C NMR (CDCl₃, 125 MHz) δ 57.7, 57.6, 48.5, 41.3, 27.9
HRMS (ESI) m/z calcd. for C₅H₉NO₂S [M+H]⁺ : 148.0427, Found: 148.0426
SI, p. S1-53
Sultone
Identifier 15
¹H NMR (CDCl₃, 500 MHz) δ 3.34 (t, J = 7.5 Hz, 2H), 2.45 (t, J = 7.5 Hz, 2H), 1.56 (s, 6H)
¹³C NMR (CDCl₃, 125 MHz) δ 88.9, 46.0, 36.1, 28.4
HRMS (ESI) m/z calcd. for C₅H₁₀O₃S [M+H]⁺ : 151.0423, Found: 151.0422
SI, p. S1-54
Desloratadine-derived material
Identifier 16
¹H NMR (CDCl₃, 500 MHz) δ 8.41 – 8.36 (m, 1H), 8.17 (d, J = 2.2 Hz, 1H), 8.07 (dd, J = 8.8, 2.3 Hz, 1H), 7.43 (dd, J = 7.7, 1.6 Hz, 1H), 7.16 (d, J = 2.1 Hz, 1H), 7.13 – 7.05 (m, 3H), 6.97 (d, J = 8.8 Hz, 1H), 4.33 (t, J = 6.0 Hz, 2H), 3.88 (d, J = 6.4 Hz, 2H), 3.57 – 3.44 (m, 2H), 3.42 – 3.28 (m, 2H), 3.19 (dtd, J = 11.5, 7.7, 7.2, 3.4 Hz, 2H), 2.98 (t, J = 7.5 Hz, 2H), 2.89 – 2.78 (m, 2H), 2.76 (s, 3H), 2.62 (ddd, J = 13.2, 8.4, 4.2 Hz, 1H), 2.50 (ddd, J = 13.0, 8.2, 4.2 Hz, 1H), 2.44 – 2.35 (m, 2H), 2.26 – 2.14 (m, 1H), 1.98 (q, J = 7.9, 7.5 Hz, 2H), 1.92 (q, J = 7.4, 6.8 Hz, 2H), 1.08 (d, J = 6.6 Hz, 6H)
¹³C NMR (CDCl₃, 125 MHz) δ 162.7, 162.1, 161.7, 156.8, 146.9, 139.7, 137.8, 137.6, 136.0, 135.3, 133.5, 133.3, 132.8, 132.3, 130.5, 129.2, 126.4, 126.1, 122.6, 121.5, 115.5, 112.8, 103.2, 75.9, 64.4, 49.2, 47.3, 31.8, 31.7, 31.0, 30.8, 28.3, 27.7, 20.3, 19.2, 17.7
HRMS (ESI) m/z calcd. for C₃₉H₄₁ClN₄O₅S₂ [M+H]⁺ : 745.2280, found: 745.2280
SI, p. S1-54
Covalent warhead
Identifier AM3506
¹H NMR (CDCl₃, 500 MHz) δ 7.04 – 6.99 (m, 2H), 6.78 – 6.72 (m, 2H), 4.65 (s, 1H), 3.36 – 3.29 (m, 2H), 2.56 (t, J = 7.5 Hz, 2H), 1.96 (p, J = 7.6, Hz, 2H), 1.64 (p, J = 7.6, Hz, 2H), 1.53 – 1.44 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 153.9, 134.0, 129.6, 115.4, 51.0, 50.9, 34.6, 30.9, 27.5, 23.5
¹⁹F NMR (CDCl₃, 376 MHz) δ 53.3
HRMS (ESI) m/z calcd. for C₅H₁₀O₃S [M−H]⁻ : 245.0653, found: 245.0651
SI, p. S1-55
PEG-linked pomalidomide derivative
Identifier 21
¹H NMR (CDCl₃, 500 MHz) δ 7.42 (t, J = 7.7 Hz, 1H), 7.15 (d, 1H), 6.86 (d, J = 8.1 Hz, 1H), 6.48 (dd, J = 14.2, 6.7 Hz, 1H), 5.24 (s, 2H), 4.98 – 4.89 (m, 1H), 4.19 (dt, J = 14.3, 1.6 Hz, 1H), 4.14 – 4.03 (m, 2H), 4.00 (dt, J = 6.5, 1.3 Hz, 1H), 3.85 – 3.76 (m, 2H), 3.70 (t, J = 4.7 Hz, 2H), 3.65 (t, J = 5.9 Hz, 2H), 3.02 – 2.90 (m, 1H), 2.84 – 2.70 (m, 2H), 2.15 – 2.03 (m, 1H)
¹³C NMR (CDCl₃, 125 MHz) δ 171.1, 169.2, 169.0, 167.7, 152.0, 145.8, 135.7, 132.5, 121.5, 113.3, 111.1, 86.8, 69.1, 67.7, 67.5, 49.8, 39.4, 32.1, 22.2
HRMS (ESI) m/z calcd. for C₁₉H₂₁N₃O₆ [M+NH₄]⁺ : 405.1769, found: 405.1762
SI, p. S1-56
Sulfonyl fluoride
Identifier 21a
¹H NMR (CDCl₃, 500 MHz) δ 7.42 (t, 1H), 7.14 (d, J = 6.9 Hz, 1H), 6.87 (d, J = 8.2 Hz, 1H), 5.27 (s, 2H), 4.98 – 4.91 (m, 1H), 4.14 – 3.93 (m, 4H), 3.72 – 3.55 (m, 8H), 3.00 – 2.91 (m, 1H), 2.83 – 2.73 (m, 2H), 2.14 – 2.00 (m, 2H)
¹³C NMR (CDCl₃, 125 MHz) δ 171.2, 169.2, 169.1, 167.8, 145.8, 135.7, 132.5, 121.6, 113.2, 110.9, 71.0, 70.4, 67.9, 64.4, 60.8, 51.4, 51.3, 50.2, 49.9, 46.5, 46.4, 39.6, 32.2, 30.7, 26.3, 24.7, 24.1, 22.1
¹⁹F NMR (CDCl₃, 376 MHz) δ 58.8
HRMS (ESI) m/z calcd. for C₁₉H₂₂FN₃O₈S [M+H]⁺ : 472.1184, found: 472.1177
SI, p. S1-56
PROTAC
Identifier 22
¹H NMR (CDCl₃, 500 MHz) δ 8.36 (d, J = 7.4 Hz, 1H), 7.64 (d, J = 8.1 Hz, 2H), 7.47 – 7.35 (m, 3H), 7.20 – 7.12 (m, 4H), 7.08 (d, J = 8.0 Hz, 2H), 6.86 (t, J = 7.5 Hz, 1H), 5.45 (s, 2H), 5.27 – 5.20 (m, 2H), 5.00 – 4.82 (m, 2H), 4.18 – 3.99 (m, 2H), 3.97 – 3.81 (m, 3H), 3.76 – 3.54 (m, 8H), 3.32 – 3.26 (m, 1H), 3.14 – 3.06 (m, 2H), 3.02 – 2.88 (m, 1H), 2.82 – 2.73 (m, 2H) 2.50 – 2.39 (m, 2H), 2.13 – 2.07 (m, 3H)
¹³C NMR (CDCl₃, 125 MHz) δ 171.2, 169.2, 169.0, 167.8, 158.7, 157.9, 156.5, 155.8, 154.2, 145.8, 135.7, 130.1, 130.1, 128.0, 124.2, 121.5, 119.7, 119.3, 113.3, 98.8, 70.8, 70.1, 67.8, 65.1, 53.7, 50.8, 49.9, 45.0, 39.5, 32.2, 31.4, 22.2, 0.1
HRMS (ESI) m/z calcd. for C₄₁H₄₃N₉O₉S [M+H]⁺: 838.2977, found: 838.2970
SI, p. S1-57
S(VI)-Pro-OH derivative
Identifier FS-Pro-OH + TMG
Cyclic voltammetry conditions CHI620A; three-electrode configuration: glassy carbon working electrode, platinum wire counter electrode, Ag/AgNO₃ reference electrode (0.1 M AgNO₃ in MeCN); 20–40 mM, 1.0 equiv. TMG to generate the corresponding carboxylates in-situ; MeCN, TBAPF₆ 0.25 M; N₂ sparge 5 min; 100 mV s⁻¹
Onset determination Irreversible event; onset potential determined graphically by extrapolating a tangent along the rising portion of the corresponding wave to the local background current
Potential reference Ferrocene internal standard; Fc/Fc⁺ midpoint assigned to 0.00 V; Fc/Fc⁺ observed at approximately +0.07 V vs. Ag/AgNO₃; potentials converted to the Fc/Fc⁺ scale by subtracting approximately 0.07 V; reported onset referenced to Fc/Fc⁺
Onset redox potential 0.74V vs. Ag/AgNO₃ → 0.67 V vs Fc/Fc⁺
SI, pp. S1-58, S1-62
S(VI)-Pro-OH derivative
Identifier Ts-Pro-OH + TMG
Cyclic voltammetry conditions CHI620A; three-electrode configuration: glassy carbon working electrode, platinum wire counter electrode, Ag/AgNO₃ reference electrode (0.1 M AgNO₃ in MeCN); 20–40 mM, 1.0 equiv. TMG to generate the corresponding carboxylates in-situ; MeCN, TBAPF₆ 0.25 M; N₂ sparge 5 min; 100 mV s⁻¹
Onset determination Irreversible event; onset potential determined graphically by extrapolating a tangent along the rising portion of the corresponding wave to the local background current
Potential reference Ferrocene internal standard; Fc/Fc⁺ midpoint assigned to 0.00 V; Fc/Fc⁺ observed at approximately +0.07 V vs. Ag/AgNO₃; potentials converted to the Fc/Fc⁺ scale by subtracting approximately 0.07 V; reported onset referenced to Fc/Fc⁺
Onset redox potential 0.56V vs. Ag/AgNO₃ → 0.49 V vs Fc/Fc⁺
SI, pp. S1-58, S1-62
S(VI)-Pro-OH derivative
Identifier Tf-Pro-OH + TMG
Cyclic voltammetry conditions CHI620A; three-electrode configuration: glassy carbon working electrode, platinum wire counter electrode, Ag/AgNO₃ reference electrode (0.1 M AgNO₃ in MeCN); 20–40 mM, 1.0 equiv. TMG to generate the corresponding carboxylates in-situ; MeCN, TBAPF₆ 0.25 M; N₂ sparge 5 min; 100 mV s⁻¹
Onset determination Irreversible event; onset potential determined graphically by extrapolating a tangent along the rising portion of the corresponding wave to the local background current
Potential reference Ferrocene internal standard; Fc/Fc⁺ midpoint assigned to 0.00 V; Fc/Fc⁺ observed at approximately +0.07 V vs. Ag/AgNO₃; potentials converted to the Fc/Fc⁺ scale by subtracting approximately 0.07 V; reported onset referenced to Fc/Fc⁺
Onset redox potential 0.76V vs. Ag/AgNO₃ → 0.69 V vs Fc/Fc⁺