Compound characterization data — Masson et al., 2026

Thibaut Masson, Corinne Landras Guetta, Charles-Henri Buffet, Tommaso Boselli, Benoît Arnould, Fabrice Leclerc, Valentina Pirota, Laurent Cattiaux, Christine Saint-Pierre, Rahima Chennoufi, Julien Gros, Gaëlle Fontaine, Sophie Bombard, Mariella Mella, Didier Gasparutto, Filippo Doria, Mauro Freccero, Daniela Verga. “Alkyldiazirine warheads for G-quadruplex photoaffinity labelling by N,O-alkylation on thymine and guanine nucleobases.” ChemRxiv (2026). https://doi.org/10.26434/chemrxiv-2026-0v374/v2

4-((2-aminoethyl)amino)-N2,N6-di(quinolin-3-yl)pyridine-2,6-dicarboxamide
Mp	dec. > 165 °C
¹H NMR (300 MHz, DMSO-d₆)	δ (ppm): 11.29 (s, 2H), 9.36 (d, J = 2.3 Hz, 2H), 8.96 (d, J = 2.3 Hz, 2H), 8.04 (d, J = 8.7 Hz, 4H), 7.72 (t, J = 7.3 Hz, 2H), 7.64 (t, J = 7.8 Hz, 2H), 7.60 - 7.48 (m, 3H), 3.29 – 3.21 (m, 2H), 2.80 (t, J = 6.3 Hz, 2H)
¹³C NMR (75 MHz, DMSO-d₆)	δ (ppm): 163.19, 156.51, 146.11, 144.67, 131.97, 128.70, 127.91, 127.76, 127.20, 124.15, 45.63
LC/MS (Method A)	Retention time 4.96 min, m/z (ESI+) = 478.3 [M-H]⁺

4-((2-(2-(2-aminoethoxy)ethoxy)ethyl)amino)-N2,N6-di(quinolin-3-yl)pyridine-2,6-dicarboxamide
Mp	dec. > 128 °C
¹H NMR (300 MHz, DMSO-d₆)	δ (ppm): 11.29 (s, 2H), 9.36 (d, J = 2.3 Hz, 2H), 8.97 (d, J = 2.1 Hz, 2H), 8.05 (d, J = 8.6 Hz, 4H), 7.72 (dt, J = 7.0, 1.1 Hz, 2H), 7.67 – 7.56 (m, 5H), 3.66 (t, J = 5.2 Hz, 2H), 3.62 – 3.51 (m, 4H), 3.50 – 3.41 (m, 2H), 3.36 (t, J = 4.8 Hz, 2H), 2.64 (t, J = 5.8 Hz, 2H)
¹³C NMR (75 MHz, DMSO-d₆)	δ (ppm): 163.18, 156.45, 146.10, 144.67, 131.99, 128.70, 128.34, 127.91, 127.76, 127.20, 124.14, 72.62, 69.87, 69.64, 68.72, 42.06, 41.15
LC/MS (Method A)	Retention time 5.93 min , m/z (ESI+) = 566.6 [M-H]⁺

Pent-4-ynal
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 9.75 (s, 1H), 2.65 (t, J = 7.0 Hz, 2H), 2.53 – 2.41 (m, 4H), 2.25 (bs, 1H)

Ethyl 4-oxooct-7-ynoate
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 4.08 (q, J = 7.1 Hz, 2H), 2.76 – 2.64 (m, 4H), 2.55 (t, J = 6.3 Hz, 2H), 2.42 (td, J = 7.3, 2.5 Hz, 2H), 1.91 (t, J = 2.6 Hz, 1H), 1.21 (t, J = 7.1 Hz, 3H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): δ 206.75, 172.81, 68.88, 60.84, 41.48, 37.22, 28.06, 14.31, 13.05

4-oxooct-7-ynoic acid
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 2.77 – 2.62 (m, 6H), 2.47 (td, J = 7.2, 2.5 Hz, 2H), 1.95 (t, J = 2.6 Hz, 1H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 206.50, 178.68, 82.97, 68.98, 41.39, 36.93, 27.80, 13.05

3-(3-(but-3-yn-1-yl)-3H-diazirin-3-yl)propanoic acid
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 2.18 (t, J = 7.7 Hz, 2H), 2.06 – 1.97 (m, 3H), 1.81 (t, J = 7.6 Hz, 2H), 1.66 (t, J = 7.1 Hz, 2H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm) 177.93, 82.69, 69.46, 32.34, 28.25, 27.91, 27.61, 13.38

4-((2-(3-(3-(but-3-yn-1-yl)-3H-diazirin-3-yl)propanamido)ethyl)amino)-N2,N6-di(quinolin-3-yl)pyridine-2,6-dicarboxamide
Mp	dec. > 170 °C
¹H NMR (300 MHz, DMSO-d₆)	δ (ppm): 11.29 (s, 2H), 9.36 (d, J = 2.2 Hz , 2H), 8.97 (d, J = 2.0 Hz, 2H), 8.12 - 7.98 (m, 5H), 7.72 (t, J = 7.4 Hz, 2H), 7.67- 7.60 (m, 2H), 7.60 – 7.50 (m, 3H), 3.30 – 3.20 (m, 2H), 2.81 (t, J = 2.5 Hz, 1H), 2.01 – 1.87 (m, 4H), 1.66 (t, J = 7.7 Hz, 2H), 1.56 (t, J = 7.3 Hz, 2H)
¹³C NMR (75 MHz, DMSO-d₆)	δ (ppm): 171.05, 163.08, 156.40, 146.06, 144.64, 131.93, 128.67, 128.31, 127.88, 127.73, 127.17, 124.11, 99.51, 83.12, 31.40, 29.48, 28.23, 28.01, 12.64
LC/MS (Method A)	Retention time 7.33 min, m/z (ESI+) = 626.6 [M-H]⁺

4-((4-(3-(3-(but-3-yn-1-yl)-3H-diazirin-3-yl)propanamido)butyl)amino)-N2,N6-di(quinolin-3-yl)pyridine-2,6-dicarboxamide
Mp	dec. > 155 °C
¹H NMR (300 MHz, DMSO-d₆)	δ (ppm): δ 11.28 (s, 2H), 9.36 (d, J = 2.4 Hz, 2H), 8.96 (d, J = 2.2 Hz, 2H), 8.04 (d, J = 8.5 Hz, 4H), 7.89 (t, J = 5.5 Hz, 1H), 7.72 (dt, J = 7.7, 1.3 Hz, 2H), 7.63 (dt, J = 7.6, 1.0 Hz, 2H), 7.60 – 7.46 (m, 3H), 3.25 (q, J = 5.8 Hz, 2H), 3.10 (q, J = 6.0 Hz, 2H), 2.81 (t, J = 2.6 Hz, 1H), 1.98 (td, J = 7.4, 2.6 Hz, 2H), 1.89 (t, J = 7.6 Hz, 2H), 1.72 – 1.48 (m, 8H)
¹³C NMR (75 MHz, DMSO-d₆)	δ (ppm): 170.50, 163.14, 156.26, 146.07, 144.64, 131.94, 128.67, 128.30, 127.87, 127.73, 127.16, 124.11, 99.52, 83.15, 71.72, 41.70, 38.12, 31.45, 29.51, 28.26, 28.13, 26.66, 25.55, 12.65
LC/MS (Method A)	Retention time 6.61 min, m/z (ESI+) = 654.6 [M-H]⁺

4-((2-(2-(2-(3-(3-(but-3-yn-1-yl)-3H-diazirin-3-yl)propanamido)ethoxy)ethoxy)ethyl)amino)-N2,N6-di(quinolin-3-yl)pyridine-2,6-dicarboxamide
Mp	dec. > 58 °C
¹H NMR (300 MHz, DMSO-d₆)	δ (ppm): 11.28 (s, 2H), 9.36 (d, J = 2.3 Hz, 2H), 8.97 (d, J = 2.4 Hz, 2H), 8.04 (d, J = 8.4 Hz, 4H), 7.73 – 7.57 (m, 8H), 3.65 – 3.53 (m, 7H), 3.43 – 3.40 (m, 3H), 3.21 – 3.16 (m, 2H), 2.80 (t, J = 2.5 Hz, 1H), 1.99 – 1.86 (m, 4H), 1.61 -1.51 (m, 4H)
¹³C NMR (75 MHz, DMSO-d₆)	δ (ppm): 170.71, 163.10, 163.03, 156.39, 148.76, 145.97, 145.89, 144.52, 131.93, 131.83, 128.56, 128.30, 127.84, 127.71, 127.15, 124.16, 124.05, 83.12, 71.64, 69.76, 69.56, 69.08, 68.65, 42.01, 31.38, 29.36, 28.18, 28.09, 12.61
LC/MS (Method A)	Retention time 6.37 min, m/z (ESI+) = 714.4 [M-H]⁺

PDC-2-N2
Mp	dec. > 184 °C
¹H NMR (300 MHz, DMSO-d₆)	δ (ppm): 11.73 (s, 2H), 10.13 (s, 2H), 9.66 (s, 2H), 8.62 – 8.48 (m, 4H), 8.23 (t, J = 7.8 Hz, 2H), 8.14 – 8.03 (m, 3H), 7.77 -7.55 (m, 3H), 4.78 (s, 6H), 3.31 – 3.24 (m, 2H), 2.81 (t, J = 2.7 Hz, 1H), 2.55 (t, J = 5.6 Hz, 2H), 2.01 – 1.88 (m, 4H), 1.67 (t, J = 7.7 Hz, 2H), 1.56 (t, J = 7.4 Hz, 2H)
¹³C NMR (75 MHz, DMSO-d₆)	δ (ppm) 171.14, 163.17, 156.74, 144.75, 135.69, 134.10, 133.94, 132.39, 130.36, 129.89, 129.24, 119.25, 83.16, 71.79, 46.19, 41.40, 37.83, 31.43, 29.51, 28.28, 28.01, 12.69
LC/MS (Method A)	Retention time 7.79 min, m/z (ESI+) = 654.6 [M-2I-H]⁺
UHPLC (Method B)	Retention time 5.46 min
HRMS (ESI, m/z)	calcd. for formula C₃₇H₃₇IN₉O₃⁺ [M-I]⁺ = 782.2064; found = 782.2084

PDC-4-N2
Mp	dec. > 190 °C
¹H NMR (300 MHz, DMSO-d₆)	δ (ppm): 11.69 (s, 2H), 10.16 (s, 2H), 9.65 (s, 2H), 8.54 (t, J = 9.2 Hz, 4H), 8.21 (t, J = 7.8 Hz, 2H), 8.05 (t, J = 7.5 Hz, 2H), 7.90 (t, J = 5.1 Hz, 1H), 7.73 - 7.38 (m, 3H), 4.78 (s, 6H), 3.31 – 3.23 (m, 2H), 3.17 – 3.03 (m, 2H), 2.82 (t, J = 2.2 Hz, 1H), 1.98 (td, J = 7.3, 2.4 Hz, 2H), 1.90 (t, J = 7.6 Hz, 2H), 1.72 – 1.47 (m, 8H)
¹³C NMR (75 MHz, DMSO-d₆)	δ (ppm): 170.54, 163.17, 156.50, 144.69, 135.61, 133.99, 133.89, 132.34, 130.29, 129.84, 129.19, 119.18, 83.16, 71.75, 46.19, 41.75, 38.10, 31.47, 29.53, 28.28, 28.13, 26.70, 25.48, 12.68
LC/MS (Method A)	Retention time 4.84 min, m/z (ESI+) = 682.6 [M-2I-H]⁺
UHPLC (Method B)	Retention time 5.71 min
HRMS (ESI, m/z)	calcd. for formula C₃₉H₄₁IN₉O₃⁺ [M-I]⁺ = 810.2377; found = 810.2339

PDC-DEG-N2
Mp	dec. > 134 °C
¹H NMR (300 MHz, DMSO-d₆)	δ (ppm): 11.72 (s, 2H), 10.10 (d, J = 2.2 Hz, 2H), 9.63 (d, J = 2.2 Hz, 2H), 8.56 (d, J = 8.9 Hz, 4H), 8.24 (t, J = 8.7 Hz, 1H), 8.08 (t, J = 7.6 Hz, 2H), 7.92 (t, J = 5.7 Hz, 1H), 7.77 (t, J = 5.8 Hz, 1H), 7.71 – 7.57 (m, 2H), 4.78 (s, 6H), 3.66 (t, J = 5.2 Hz, 2H), 3.62 – 3.51 (m, 3H), 3.51 – 3.37 (m, 3H), 3.20- 3.12 (m, 2H), 2.82 (t, J = 2.6 Hz, 1H), 2.60 – 2.50 (m, 1H), 1.99 – 1.83 (m, 4H), 1.64 – 1.47 (m, 4H)
¹³C NMR (75 MHz, DMSO-d₆)	δ (ppm): 170.81, 163.23, 156.78, 144.76, 135.70, 134.13, 133.97, 132.43, 130.39, 129.90, 129.26, 119.26, 71.79, 69.87, 69.63, 69.13, 68.78, 46.21, 42.16, 38.57, 31.41, 29.43, 28.28, 28.12, 12.69
LC/MS (Method A)	Retention time 4.84 min, m/z (ESI+) = 742.6 [M-2I-H]⁺
UHPLC (Method B)	Retention time 5.60 min
HRMS (ESI, m/z)	calcd. for formula C₄₁H₄₅IN₉O₅⁺ [M-I]⁺ = 870.2588; found = 870.2582

Methyl 4-(prop-2-yn-1-ylamino)butanoate
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 3.66 (s, 3H), 3.41 (d, J = 2.4 Hz, 2H), 2.72 (t, J = 7.0 Hz, 2H), 2.38 (t, J = 7.4 Hz, 2H), 2.20 (t, J = 2.4 Hz, 1H), 1.81 (p, J = 7.2 Hz, 2H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 174.10, 82.26, 71.42, 51.70, 47.85, 38.12, 31.93, 25.07

Methyl 4-(pent-4-yn-1-ylamino)butanoate
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 3.70 (s, 3H), 3.19 – 3.08 (m, 4H), 2.55 (t, J = 6.9 Hz, 2H), 2.41 (td, J = 6.7, 2.5 Hz, 2H), 2.31 – 2.11 (m, 4H), 2.03 (t, J = 2.6 Hz, 1H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 172.88, 81.79, 70.45, 52.07, 47.29, 46.88, 31.16, 24.52, 21.09, 16.23

Methyl 4-(N-(prop-2-yn-1-yl)-4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzamido)butanoate
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 7.62 – 7.38 (m, 2H), 7.25 – 7.20 (m, 2H), 4.36 (bs, 1H), 3.95 (bs, 1H), 3.72 – 3.34 (m, 5H), 2.49 – 2.14 (m, 3H), 2.10 – 1.82 (m, 2H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 170.22, 136.99, 130.91, 127.43, 126.74, 123.83, 120.19, 116.55, 78.51, 73.44, 72.22, 51.77, 47.80, 44.92, 39.41, 33.95, 31.37, 28.66, 28.12, 23.30, 22.37
LC/MS (Method A)	Retention time 6.19 min, m/z (ESI+) = 368.1 [M-H]⁺

Methyl 4-(4-azido-2,3,5,6-tetrafluoro-N-(prop-2-yn-1-yl)benzamido)butanoate
¹H NMR (300 MHz, CDCl₃)	Presence of two conformers: δ (ppm): 4.39 (d, J = 2.5 Hz, 1H), 3.99 (d, J = 2.4 Hz, 1H), 3.75 -3.56 (m, 4H), 3.50 -3.31 (m, 1H), 2.43 (t, J = 7.3 Hz, 1H), 2.34 – 2.24 (m, 2H), 2.04 (p, J = 7.2 Hz, 1H), 1.90 (p, J = 6.9 Hz, 1H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 173.44, 172.88, 159.02, 144.50, 142.41, 142.17, 141.18, 139.07, 138.85, 121.66, 111.06, 77.41, 76.80, 73.89, 73.04, 51.85, 51.79, 47.40, 45.17, 38.65, 34.15, 31.01, 29.87, 22.85, 22.40
LC/MS (Method A)	Retention time 6.50 min, m/z (ESI+) = 373.1 [M-H]⁺

Methyl 4-(4-benzoyl-N-(prop-2-yn-1-yl)benzamido)butanoate
¹H NMR (300 MHz, CDCl₃)	Presence of two conformers: δ (ppm): 7.93 – 7.74 (m, 4H), 7.70 – 7.41 (m, 5H), 4.40 (bs, 1H), 4.00 (bs, 1H), 3.80 – 3.37 (m, 5H), 2.54 – 1.84 (m, 5H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 196.09, 170.61, 139.39, 138.91, 137.17, 132.95, 130.30, 130.21, 128.56, 126.84, 78.57, 51.86, 47.87, 46.41, 44.90, 39.47, 33.96, 32.01, 31.46, 30.77, 23.37, 22.46
LC/MS (Method A)	Retention time 6.74 min, m/z (ESI+) = 364.2 [M-H]⁺

Methyl 4-(N-(pent-4-yn-1-yl)-4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzamido)butanoate
¹H NMR (300 MHz, CDCl₃)	Presence of two conformers: δ (ppm): 7.38 (d, J = 8.3 Hz, 2H), 7.20 (d, J = 8.1 Hz, 2H), 3.71 – 3.43 (m, 5H), 3.33 - 3.13 (m, 2H), 2.45 – 2.08 (m, 3H), 2.06 – 1.62 (m, 6H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 170.74, 138.15, 130.32, 127.21, 126.81, 123.92, 120.28, 69.48, 69.31, 51.83, 48.78, 48.17, 44.26, 31.38, 27.51, 22.84, 16.33, 15.96
LC/MS (Method A)	Retention time 6.86 min, m/z (ESI+) = 396.4 [M-H]⁺

Methyl 4-(4-azido-2,3,5,6-tetrafluoro-N-(pent-4-yn-1-yl)benzamido)butanoate
¹H NMR (300 MHz, CDCl₃)	Presence of two conformers: δ (ppm): 3.72 – 3.54 (m, 5H), 3.36 – 3.22 (m, 2H), 2.45 – 2.36 (m, 1H), 2.32 – 2.20 (m, 2H), 2.14 (td, J = 6.6, 2.5 Hz, 1H), 2.04 – 1.78 (m, 4H), 1.72 (p, J = 6.9 Hz, 1H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 173.49, 172.81, 159.11, 159.07, 144.40, 142.43, 142.21, 141.16, 139.05, 138.89, 83.17, 82.19, 69.72, 69.47, 69.40, 51.93, 51.86, 51.82, 48.25, 47.48, 46.10, 46.05, 45.71, 45.66, 44.54, 44.36, 31.00, 30.85, 30.03, 27.09, 26.53, 26.49, 26.07, 23.40, 22.93, 22.88, 22.58, 16.05, 15.99, 15.55
LC/MS (Method A)	Retention time 6.77 min, m/z (ESI+) = 401.5 [M-H]⁺

Methyl 4-(4-benzoyl-N-(pent-4-yn-1-yl)benzamido)butanoate
¹H NMR (300 MHz, CDCl₃)	Presence of two conformers: δ (ppm): 7.87 – 7.76 (m, 4H), 7.67 – 7.57 (m, 1H), 7.55 – 7.41 (m, 4H), 3.80 - 3.47 (m, 5H), 2.52 - 2.38 (m, 1H), 2.37 – 2.26 (m, 1H), 2.24 - 2.12 (m, 1H), 2.12 – 1.65 (m, 6H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 196.13, 171.03, 140.52, 138.39, 137.22, 132.90, 130.30, 130.19, 128.53, 126.55, 69.59, 69.31, 53.56, 51.84, 48.76, 48.17, 44.25, 31.39, 30.80, 27.50, 26.35, 23.95, 22.85, 16.30, 15.84
LC/MS (Method A)	Retention time 6.54 min, m/z (ESI+) = 392.3 [M-H]⁺

4-(N-(prop-2-yn-1-yl)-4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzamido)butanoic acid
¹H NMR (300 MHz, CDCl₃)	Presence of two conformers: δ (ppm): 7.62 – 7.42 (m, 2H), 7.24 -7.20 (m, 2H), 4.48 – 4.24 (m, 1H), 4.02 – 3.88 (m, 1H), 3.76 – 3.61 (m, 1H), 3.55 – 3.35 (m, 1H), 2.51 – 2.19 (m, 3H), 2.10 – 1.85 (m, 2H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 178.39, 177.85, 170.55, 136.66, 131.09, 127.45, 126.70, 123.83, 120.19, 116.54, 78.39, 47.82, 44.97, 39.50, 34.10, 31.57, 28.67, 28.13, 22.22
LC/MS (Method A)	Retention time 6.05 min, m/z (ESI+) = 354.1 [M-H]⁺

4-(4-azido-2,3,5,6-tetrafluoro-N-(prop-2-yn-1-yl)benzamido)butanoic acid
¹H NMR (300 MHz, CDCl₃)	Presence of two conformers: δ (ppm): 4.39 (d, J = 2.3 Hz, 1H), 3.98 (d, J = 2.0 Hz, 1H), 3.74 (t, J = 7.1 Hz, 1H), 3.48 – 3.35 (m, 1H), 2.48 (t, J = 7.3 Hz, 1H), 2.40 – 2.29 (m, 2H), 2.04 (p, J = 7.3 Hz, 1H), 1.94 - 1.82 (m, 1H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 178.72, 159.28, 159.09, 144.50, 142.41, 142.18, 141.25, 139.08, 138.85, 110.98, 99.86, 97.62, 88.03, 77.43, 74.02, 73.17, 47.37, 45.13, 38.75, 34.39, 31.02, 29.79, 22.73, 22.17
LC/MS (Method A)	Retention time 6.01 min, m/z (ESI+) = 359.0 [M-H]⁺

4-(4-benzoyl-N-(prop-2-yn-1-yl)benzamido)butanoic acid
¹H NMR (300 MHz, CDCl₃)	Presence of two conformers: δ (ppm): 7.88 – 7.74 (m, 4H), 7.67 – 7.43 (m, 5H), 4.40 (bs, 1H), 4.01 (bs, 1H), 3.80 – 3.35 (m, 2H), 2.56 – 2.16 (m, 3H), 2.11 – 1.83 (m, 2H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 196.16, 170.86, 139.11, 137.12, 133.00, 130.31, 130.23, 128.58, 126.88, 78.47, 47.87, 44.93, 39.57, 34.10, 31.45, 22.31
LC/MS (Method A)	Retention time 5.82 min, m/z (ESI+) = 350.4 [M-H]⁺

4-(N-(pent-4-yn-1-yl)-4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzamido)butanoic acid
¹H NMR (300 MHz, CDCl₃)	Presence of two conformers: δ (ppm): 7.41 (d, J = 8.4 Hz, 2H), 7.25 – 7.19 (m, 2H), 3.63 – 3.53 (m, 2H), 3.41 – 3.21 (m, 2H), 2.54 – 2.41 (m, 1H), 2.36 – 2.17 (m, 2H), 2.09 – 1.67 (m, 6H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 177.89, 171.02, 137.82, 130.43, 127.21, 126.79, 123.90, 120.26, 69.56, 48.77, 48.20, 45.37, 44.43, 31.49, 30.75, 28.17, 27.43, 26.28, 23.68, 22.74, 16.29, 15.79
LC/MS (Method A)	Retention time 6.28 min, m/z (ESI+) = 382.4 [M-H]⁺

4-(4-azido-2,3,5,6-tetrafluoro-N-(pent-4-yn-1-yl)benzamido)butanoic acid
¹H NMR (300 MHz, CDCl₃)	Presence of two conformers: δ (ppm): 3.65 – 3.58 (m, 2H), 3.35 – 3.26 (m, 2H), 2.47 (t, J = 7.2 Hz, 1H), 2.35 – 2.27 (m, 2H), 2.19 – 2.10 (m, 1H), 2.06 – 1.62 (m, 5H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 178.00, 159.43, 144.55, 142.22, 141.20, 139.12, 112.16, 83.19, 82.15, 69.54, 48.29, 47.52, 44.62, 44.50, 30.86, 29.79, 27.11, 26.15, 23.23, 22.42, 16.04, 15.56
LC/MS (Method A)	Retention time 6.17 min, m/z (ESI+) = 387.3 [M-H]⁺

4-(4-benzoyl-N-(pent-4-yn-1-yl)benzamido)butanoic acid
¹H NMR (300 MHz, CDCl₃)	Presence of two conformers: δ (ppm): 7.80 (t, J = 7.5 Hz, 4H), 7.64 – 7.57 (m, 1H), 7.48 (t, , J = 8.0 Hz, 4H), 3.66 – 3.51 (m, 2H), 3.41 – 3.23 (m, 2H), 2.51 -2.41 (m, , 1H), 2.36 – 2.26 (m, 1H), 2.23 – 2.14 (m, 1H), 2.12 – 1.66 (m, 6H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 196.18, 177.88, 177.37, 171.36, 140.20, 138.46, 137.17, 132.96, 130.33, 130.22, 128.56, 126.58, 82.34, 69.69, 48.71, 48.22, 44.39, 31.46, 27.46, 26.33, 22.75, 16.30, 15.85
LC/MS (Method A)	Retention time 6.03 min, m/z (ESI+) = 378.3 [M-H]⁺

2-(2-(prop-2-yn-1-yloxy)ethoxy)ethan-1-ol
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 4.21 (d, J = 2.4 Hz, 2H), 3.78 – 3.66 (m, 6H), 3.65 - 3.58 (m, 2H), 2.44 (t, J = 2.4 Hz, 1H), 2.32 (t, J = 6.1 Hz, 1H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 79.45, 74.82, 72.57, 70.11, 69.08, 61.58, 58.36

2-(2-(2-(prop-2-yn-1-yloxy)ethoxy)ethoxy)ethan-1-ol
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 4.21 (d, J = 2.4 Hz, 2H), 3.77 – 3.64 (m, 10H), 3.63 – 3.57 (m, 2H), 2.48 (bs, 1H), 2.43 (t, J = 2.3 Hz, 1H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 79.65, 74.75, 72.60, 70.72, 70.47, 70.42, 69.16, 61.83, 58.51

3-(2-(2-bromoethoxy)ethoxy)prop-1-yne
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 4.22 (d, J = 2.4 Hz, 2H), 3.82 (t, J = 6.3 Hz, 2H), 3.71 (s, 4H), 3.48 (t, J = 6.3 Hz, 2H), 2.44 (t, J = 2.4 Hz, 1H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 79.63, 74.77, 71.34, 70.46, 69.18, 58.60, 30.32

3-(2-(2-(2-bromoethoxy)ethoxy)ethoxy)prop-1-yne
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 4.20 (d, J = 2.4 Hz, 2H), 3.81 (t, J = 6.3 Hz, 2H), 3.71 – 3.63 (m, 8H), 3.47 (t, J = 6.3 Hz, 2H), 2.43 (t, J = 2.4 Hz, 1H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 79.71, 74.66, 71.30, 70.71, 70.61, 70.58, 69.20, 58.51, 30.43

4-ethoxy-4-oxobutan-1-amonium
¹H NMR (300 MHz, DMSO-d₆)	δ (ppm): 8.10 (bs, 1H), 4.06 (q, J = 7.1 Hz, 2H), 2.81 – 2.74 (m, 2H), 2.41 (t, J = 7.5 Hz, 2H), 1.80 (p, J = 7.5 Hz, 2H), 1.18 (t, J = 7.1 Hz, 3H)
¹³C NMR (75 MHz, DMSO-d₆)	δ (ppm): 172.20, 59.98, 38.01, 30.44, 22.40, 14.12

Ethyl 4-((2-(2-(prop-2-yn-1-yloxy)ethoxy)ethyl)amino)butanoate
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 4.21 (d, J = 2 .4 Hz, 2H), 4.12 (q, J = 7.1 Hz, 2H), 3.98 - 3.85 (m, 2H), 3.72 (s, 4H), 3.29 - 3.18 (m, 2H), 3.13 (t, J = 7.4 Hz, 2H), 2.55 - 2.37 (m, 4H), 2.15 (p, J = 7.0 Hz, 2H), 1.25 (t, J = 7.1 Hz, 3H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 172.81, 79.24, 75.14, 69.98, 68.91, 65.98, 60.84, 58.34, 47.43, 47.30, 31.30, 21.30, 14.12

Ethyl 4,7,10-trioxa-13-azaheptadec-1-yn-17-oate
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 4.17 (d, J = 2.4 Hz, 2H), 4.07 (q, J = 7.1 Hz, 2H), 3.88 (t, J = 5.0 Hz, 2H), 3.71 – 3.57 (m, 8H), 3.19 (t, J = 5.0 Hz, 2H), 3.10 (t, J = 7.6 Hz, 2H), 2.48 – 2.37 (m, 3H), 2.19 – 2.05 (m, 2H), 1.20 (t, J = 7.1 Hz, 3H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 172.65, 79.50, 74.96, 70.20, 70.16, 70.13, 68.89, 65.78, 60.85, 58.42, 47.32, 47.22, 31.33, 21.15, 14.17

Ethyl 4-(N-(2-(2-(prop-2-yn-1-yloxy)ethoxy)ethyl)-4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzamido) butanoate
¹H NMR (300 MHz, CDCl₃)	Presence of two conformers: δ (ppm): 7.51 – 7.36 (m, 2H), 7.21 (d, J = 8.1 Hz, 2H), 4.21 - 3.98 (m, 4H), 3.78 - 3.27 (m, 10H), 2.48 - 2.35 (m, 2H), 2.17 – 2.07 (m, 1H), 2.05 – 1.92 (m, 1H), 1.90 – 1.77 (m, 1H), 1.28 - 1.16 (m, 3H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 173.23, 172.42, 171.13, 170.75, 138.13, 130.25, 130.18, 130.04, 127.68, 127.18, 126.57, 126.30, 123.85, 120.21, 116.57, 79.51, 74.79, 70.38, 69.11, 68.54, 60.57, 58.45, 49.56, 48.88, 44.87, 44.63, 31.59, 31.05, 28.64, 28.10, 23.77, 22.69, 14.23
LC/MS (Method A)	Retention time 6.92 min, m/z (ESI+) = 470.0 [M-H]⁺, 492.0 [M-Na-H]⁺

Ethyl 4-(4-azido-2,3,5,6-tetrafluoro-N-(2-(2-(prop-2-yn-1-yloxy)ethoxy)ethyl)benzamido)butanoate
¹H NMR (300 MHz, CDCl₃)	Presence of two conformers: δ (ppm): 4.21 - 4.00 (m, 4H), 3.80 - 3.49 (m, 8H), 3.44 – 3.33 (m, 2H), 2.45 – 2.36 (m, 2H), 2.21 (t, J = 6.8 Hz, 1H), 1.99 (p, J = 7.3 Hz, 1H), 1.83 (p, J = 7.0 Hz, 1H), 1.31 – 1.19 (m, 3H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 173.01, 172.43, 159.44, 159.12, 144.37, 144.29, 142.33, 142.27, 142.16, 142.11, 141.24, 141.07, 141.00, 140.83, 138.96, 138.91, 138.80, 138.74, 120.86, 112.42, 112.13, 111.88, 111.60, 79.57, 79.42, 74.66, 74.62, 70.53, 70.40, 69.05, 68.98, 68.44, 60.58, 60.55, 58.41, 58.36, 49.19, 48.77, 45.32, 45.02, 31.18, 30.27, 23.22, 22.50, 14.24, 14.12
LC/MS (Method A)	Retention time 6.81 min, m/z (ESI+) = 475.0 [M-H]⁺, 497.0 [M-Na]⁺

Ethyl 4-(4-benzoyl-N-(2-(2-(prop-2-yn-1-yloxy)ethoxy)ethyl)benzamido)butanoate
¹H NMR (300 MHz, CDCl₃)	Presence of two conformers: δ (ppm): 7.82 (t, J = 7.0 Hz, 4H), 7.65 – 7.45 (m, 5H), 4.22 – 3.98 (m, 4H), 3.81 – 3.32 (m, 10H), 2.42 (d, J = 7.2 Hz, 2H), 2.15 (t, J = 7.4 Hz, 1H), 2.02 (t, J = 7.5 Hz, 1H), 1.86 (t, J = 7.6 Hz, 1H), 1.24 (dt, J = 23.3 Hz, 7.2 Hz, 3H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 196.13, 173.23, 172.46, 171.38, 171.04, 140.63, 140.49, 138.24, 138.11, 137.23, 132.76, 130.12, 128.45, 127.01, 126.52, 74.81, 70.40, 69.11, 68.70, 60.58, 58.45, 49.55, 48.83, 44.85, 44.67, 31.61, 31.06, 23.79, 22.72, 14.29
LC/MS (Method A)	Retention time 6.56 min, m/z (ESI+) = 466.0 [M-H]⁺, 488.0 [M-Na]⁺

Ethyl 13-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoyl)-4,7,10-trioxa-13-azaheptadec-1-yn-17-oate
¹H NMR (300 MHz, CDCl₃)	Presence of two conformers: δ (ppm): 7.50 – 7.39 (m, 2H), 7.21 (d, J = 7.4 Hz, 2H), 4.20 – 4.09 (m, 3H), 4.07 – 3.97 (m, 1H), 3.75 – 3.48 (m, 11H), 3.44 -3.27 (m, 2H), 2.46 – 2.32 (m, 2H), 2.19 – 2.07 (m, 1H), 2.04 – 1.91 (m, 1H), 1.89 – 1.63 (m, 2H), 1.32 – 1.12 (m, 3H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 173.32, 173.25, 172.47, 172.36, 171.14, 170.79, 138.24, 138.17, 130.25, 130.14, 127.71, 127.24, 126.70, 126.63, 123.91, 120.27, 79.68, 74.72, 70.72, 70.56, 69.21, 68.63, 60.64, 58.52, 49.56, 48.91, 44.95, 44.64, 31.66, 31.12, 28.70, 28.17, 23.83, 22.75, 14.32
LC/MS (Method A)	Retention time 6.87 min, m/z (ESI+) = 514.6 [M-H]⁺

Ethyl 13-(4-azido-2,3,5,6-tetrafluorobenzoyl)-4,7,10-trioxa-13-azaheptadec-1-yn-17-oate
¹H NMR (300 MHz, CDCl₃)	Presence of two conformers: δ (ppm): 4.21 – 4.00 (m, 4H), 3.77 – 3.48 (m, 12H), 3.41 – 3.32 (m, 2H), 2.44 – 2.35 (m, 2H), 2.20 (t, J = 6.8 Hz, 1H), , 1.99 (p, J = 7.3 Hz, 1H), 1.82 (p, J = 7.0 Hz, 1H), 1.30 – 1.18 (m, 3H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 173.01, 172.43, 159.44, 159.12, 144.37, 144.29, 142.33, 142.27, 142.11, 141.07, 141.00, 138.96, 138.74, 120.86, 112.42, 112.13, 111.88, 111.60, 79.57, 79.42, 74.66, 74.62, 70.53, 70.40, 69.05, 68.98, 68.44, 60.58, 60.55, 58.41, 58.36, 49.19, 48.77, 45.32, 45.02, 31.18, 30.27, 23.22, 22.50, 14.24, 14.12
LC/MS (Method A)	Retention time 7.54 min, m/z (ESI+) = 519.6 [M-H]⁺

Ethyl 13-(4-benzoylbenzoyl)-4,7,10-trioxa-13-azaheptadec-1-yn-17-oate
¹H NMR (300 MHz, CDCl₃)	Presence of two conformers: δ (ppm): 7.86 – 7.77 (m, 4H), 7.66 – 7.57 (m, 1H), 7.56 - 7.45(m, 4H), 4.24 – 3.97 (m, 4H), 3.79 – 3.52 (m, 12H), 3.50 – 3.43 (m, 1H), 3.41 -3.33 (m, 1H), 2.51 (m, 2H), 2.19 – 2.09 (m, 1H), 2.08 – 1.95 (m, 1H), 1.91 – 1.80 (m, 1H), 1.33– 1.13 (m, 3H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 196.16, 173.25, 172.48, 171.39, 171.07, 140.69, 140.55, 138.19, 137.27, 132.83, 130.26, 130.17, 128.50, 127.04, 126.57, 79.68, 74.71, 70.71, 70.53, 69.18, 68.75, 60.61, 58.48, 53.55, 49.57, 48.86, 44.90, 44.69, 31.67, 31.11, 23.84, 22.76, 14.30
LC/MS (Method A)	Retention time 6.49 min, m/z (ESI+) = 510.4 [M-H]⁺

4-(N-(2-(2-(prop-2-yn-1-yloxy)ethoxy)ethyl)-4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzamido) butanoic acid
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 7.55– 7.38 (m, 2H), 7.22 (d, J = 8.2 Hz, 2H), 4.19 (d, J = 2.5 Hz, 2H), 3.82 – 3.26 (m, 10H), 2.45 (bs, 2H), 2.27 – 2.17 (m, 1H), 2.07 – 1.95 (m, 1H), 1.92 – 1.77 (m, 1H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 177.46, 177.13, 171.53, 171.08, 137.63, 130.33, 130.26, 130.14, 127.66, 127.16, 126.51, 123.80, 120.16, 116.51, 79.40, 74.86, 70.29, 69.02, 68.41, 58.36, 49.54, 48.93, 45.02, 44.67, 31.91, 31.31, 30.61, 29.68, 29.13, 28.59, 28.06, 27.52, 23.39, 22.44
LC/MS (Method A)	Retention time 6.15 min, m/z (ESI+) = 442.0 [M-H]⁺, 464.0 [M-Na]⁺

4-(4-azido-2,3,5,6-tetrafluoro-N-(2-(2-(prop-2-yn-1-yloxy)ethoxy)ethyl)benzamido)butanoic acid
¹H NMR (300 MHz, CDCl₃)	Presence of two conformers: δ (ppm): 4.17 (dd, J = 11.1 Hz, 2.3 Hz, 2H), 3.78 – 3.46 (m, 8H), 3.42 – 3.31 (m, 2H), 2.48 – 2.41 (m, 2H), 2.30 (t, J = 6.4 Hz, 1H), 1.99 (p, J = 7.2 Hz, 1H), 1.82 (p, J = 6.6 Hz, 1H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 178.71, 178.50, 159.77, 159.36, 144.40, 142.38, 142.17, 141.11, 139.07, 138.82, 121.02, 111.83, 79.60, 79.45, 74.79, 74.76, 70.62, 70.48, 69.23, 69.13, 69.03, 68.58, 58.51, 58.46, 49.28, 48.91, 45.79, 45.09, 31.02, 29.93, 23.01, 22.35
LC/MS (Method A)	Retention time 6.26 min, m/z (ESI+) = 447.0 [M-H]⁺, 469.0 [M-Na]⁺

4-(4-benzoyl-N-(2-(2-(prop-2-yn-1-yloxy)ethoxy)ethyl)benzamido)butanoic acid
¹H NMR (300 MHz, CDCl₃)	Presence of two conformers: δ (ppm): 7.78 (t, J = 7.6 Hz, 4H), 7.60 – 7.42 (m, 5H), 4.16 (d, J = 6.7 Hz, 2H), 3.79 – 3.30 (m, 10H), 2.41 (d, J = 7.6 Hz , 2H), 2.21 – 2.10 (m, 1H), 2.04 – 1.91 (m, 1H), 1.89 – 1.72 (m, 1H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 196.18, 177.69, 177.26, 171.74, 171.31, 140.24, 138.21, 137.16, 132.83, 130.26, 130.15, 128.47, 127.04, 126.57, 79.47, 74.90, 70.37, 70.30, 69.09, 68.68, 58.43, 49.50, 48.93, 45.02, 44.73, 31.40, 30.67, 29.74, 23.49, 22.56
LC/MS (Method A)	Retention time 5.81 min, m/z (ESI+) = 438.0 [M-H]⁺, 460.0 [M-Na]⁺

13-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoyl)-4,7,10-trioxa-13-azaheptadec-1-yn-17-oic acid
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 7.50 – 7.39 (m, 2H), 7.22 (d, J = 8.0 Hz, 2H), 4.21 (d, J = 2.3 Hz, 2H), 3.78 – 3.48 (m, 13H), 3.44 – 3.32 (m, 2H), 2.50 – 2.41 (m, 2H), 2.25 – 2.15 (m, 1H), 2.08 – 1.96 (m, 1H), 1.90 – 1.78 (m, 1H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 177.36, 177.07, 171.48, 170.97, 137.92, 130.32, 127.71, 127.23, 126.66, 123.91, 120.26, 79.56, 74.86, 70.73, 70.51, 69.43, 69.19, 68.83, 58.50, 49.50, 49.06, 45.00, 44.79, 31.46, 30.79, 29.83, 28.71, 28.18, 23.56, 22.65
LC/MS (Method A)	Retention time 6.16 min, m/z (ESI+) = 486.4 [M-H]⁺

13-(4-azido-2,3,5,6-tetrafluorobenzoyl)-4,7,10-trioxa-13-azaheptadec-1-yn-17-oic acid
¹H NMR (300 MHz, CDCl₃)	Presence of two conformers: δ (ppm): 4.20 (t, J = 2.2 Hz, 2H), 3.77 – 3.47 (m, 12H), 3.43 – 3.34 (m, 2H), 2.51 – 2.40 (m, 2H), 2.30 (t, J = 6.5 Hz, 1H), 2.01 (quint, J = 7.1 Hz, 1H), 1.84 (quint, J = 7.1 Hz, 1H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 176.98, 176.85, 159.26, 144.46, 141.10, 139.06, 125.39, 70.81, 70.66, 70.48, 70.43, 70.24, 69.44, 69.22, 69.16, 68.78, 58.49, 49.22, 48.99, 45.61, 45.13, 30.97, 30.11, 23.19, 22.47
LC/MS (Method A)	Retention time 6.92 min, m/z (ESI+) = 491.5 [M-H]⁺

13-(4-benzoylbenzoyl)-4,7,10-trioxa-13-azaheptadec-1-yn-17-oic acid
¹H NMR (300 MHz, CDCl₃)	Presence of two conformers: δ (ppm): 7.81 (t, J = 6.6 Hz, 4H), 7.65 – 7.57 (m, 1H), 7.56 – 7.44 (m, 4H), 4.20 (bs, 2H), 3.82 – 3.51 (m, 12H), 3.50 – 3.34 (m, 2H), 2.52 – 2.44 (m, 1H), 2.42 (t, J = 2.4 Hz, 1H), 2.26 – 2.14 (m, 1H), 2.09 – 1.97 (m, 1H), 1.94 – 1.78 (m, 1H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 196.25, 177.23, 176.72, 171.75, 171.28, 140.39, 138.33, 137.23, 132.91, 130.22, 128.54, 127.07, 126.62, 79.58, 74.88, 70.72, 70.50, 69.44, 69.18, 68.96, 58.48, 49.47, 49.03, 44.97, 44.82, 31.50, 30.82, 23.63, 22.71
LC/MS (Method A)	Retention time 5.86 min, m/z (ESI+) = 482.4 [M-H]⁺

4-((4-(4-(N-(prop-2-yn-1-yl)-4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzamido)butanamido)butyl)amino)-N2,N6-di(quinolin-3-yl)pyridine-2,6-dicarboxamide
Mp	dec. > 104 °C
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 10.14 (s, 2H), 9.10 (d, J = 2.29 Hz, 2H), 8.83 (s, 2H), 8.04 (d, J = 7.98 Hz, 2H), 7.78 (d, J = 7.70 Hz, 2H), 7.65 (t, J = 7.20 Hz, 2H), 7.54 (t, J = 7.29 Hz, 2H), 7.45 (m, 2H), 7.13 (d, J = 7.61 Hz, 2H), 6.95 (bs, 1H), 5.78 (bs, 1H), 3.90 (bs, 2H), 3.65 - 3.60 (m, 2H), 3.39 - 3.20 (m, 5H), 2.30 - 2.24 (m, 2H), 2.04 - 1.95 (m, 3H), 1.48 - 1.40 (m, 3H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 172.80, 171.06, 163.30, 156.12, 148.94, 145.19, 144.90, 136.36, 131.44, 131.20, 131.18, 128.87, 128.65, 128.21, 127.88, 127.41, 127.19, 126.70, 124.61, 123.78, 120.14, 78.24, 66.01, 55.66, 45.06, 43.66, 42.66, 39.52, 39.15, 33.73, 29.84, 28.63, 27.25, 25.99, 23.23
LC/MS (Method A)	Retention time 6.92 min, m/z (ESI+) = 841.4 [M-H]⁺

4-((4-(4-(4-azido-2,3,5,6-tetrafluoro-N-(prop-2-yn-1-yl)benzamido)butanamido)butyl)amino)-N2,N6-di(quinolin-3-yl)pyridine-2,6-dicarboxamide
Mp	dec. > 123 °C
¹H NMR (300 MHz, DMSO-d₆)	δ (ppm): 11.29 (s, 2H), 9.36 (d, J = 2.2 Hz, 2H), 8.97 (d, J = 1.9 Hz, 2H), 8.05 (d, J = 8.4 Hz, 4H), 7.95 – 7.79 (m, 1H), 7.77 – 7.44 (m, 7H), 4.34 (d, J = 2.0 Hz, 1H), 4.13 (s, 1H), 3.55 (t, J = 7.4 Hz, 1H), 3.29 – 3.19 (m, 3H), 3.17 – 2.98 (m, 2H), 2.14 (t, J = 7.3 Hz, 1H), 2.00 (t, J = 6.8 Hz, 1H), 1.92 – 1.40 (m, 7H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 200.85, 172.59, 171.90, 163.40, 159.72, 159.29, 155.99, 155.92, 148.63, 144.67, 144.26, 142.53, 142.19, 141.94, 140.85, 138.81, 138.61, 131.61, 128.70, 128.41, 128.07, 127.80, 127.34, 126.77, 125.26, 124.96, 118.37, 110.43, 99.36, 87.95, 77.35, 76.51, 47.76, 45.36, 42.55, 39.19, 38.60, 34.04, 33.18, 31.68, 27.15, 26.00, 23.16
LC/MS (Method A)	Retention time 6.83 min, m/z (ESI+) = 846.3 [M-H]⁺

4-((4-(4-(4-benzoyl-N-(prop-2-yn-1-yl)benzamido)butanamido)butyl)amino)-N2,N6-di(quinolin-3-yl)pyridine-2,6-dicarboxamide
Mp	dec. > 122 °C
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 10.49 - 10.38 (bs, 2H), 9.25 (s, 2H), 8.85 (s, 2H), 8.03 (d, J = 8.1 Hz, 2H), 7.73 (d, J = 7.1 Hz, 6H), 7.65 – 7.60 (m, 2H), 7.53 - 7.51 (m, 5H), 7.43 - 7.38 (m, 4H), 7.06 (bs, 1H), 5.77 (bs, 1H), 3.96 (s, 1H), 3.69 (t, J = 7.47 Hz, 1H), 3.36 (bs, 1H), 3.23 (bs, 1H), 2.31 - 2.11 (m, 6H), 2.10 - 1.96 (m, 3H), 1.75 - 1.58 (m, 4H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 195.96, 172.84, 171.13, 163.44, 155.98, 148.71, 144.96, 144.52, 142.60, 138.85, 138.74, 136.82, 132.96, 131.61, 130.11, 128.60, 128.49, 128.28, 128.05, 127.78, 127.25, 126.56, 124.96, 118.47, 110.37, 78.27, 73.79, 44.93, 42.56, 39.36, 39.16, 33.70, 29.73, 27.16, 26.07, 23.20
LC/MS (Method A)	Retention time 6.87 min, m/z (ESI+) = 837.6 [M-H]⁺

4-((4-(4-(N-(pent-4-yn-1-yl)-4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzamido)butanamido)butyl)amino)-N2,N6-di(quinolin-3-yl)pyridine-2,6-dicarboxamide
Mp	dec. > 65 °C
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 10.19 (s, 2H), 9.13 (s, 2H), 8.88 (s, 2H), 8.06 (d, J = 8.34 Hz, 2H), 7.81 (d, J = 7.99 Hz, 2H), 7.66 (t, J = 7.53 Hz, 2H), 7.55 (t, J = 7.36 Hz, 2H), 7.41 (bs, 2H), 7.30 (d, J = 8.18 Hz, 2H), 7.14 - 7.01 (m, 3H), 5.78 (bs, 1H), 3.55 - 3.46 (m, 2H), 3.41 - 3.33 (m, 1H) , 3.31 - 3.20 (m, 4H), 2.30 - 2.21 (m, 2H), 2.02 - 1.86 (m, 8H), 1.70 - 1.59 (m, 4H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 172.84, 171.41, 163.46, 156.00, 148.72, 145.01, 144.69, 142.71, 137.33, 131.58, 130.25, 128.61, 128.40, 128.08, 127.81, 127.30, 126.80, 126.59, 124.86, 123.75, 120.11, 118.51, 116.47, 110.38, 82.10, 69.52, 68.31, 48.00, 44.42, 42.55, 39.17, 33.62, 28.54, 28.00, 27.16, 26.05, 23.62, 15.62
LC/MS (Method A)	Retention time 7.02 min, m/z (ESI+) = 869.4 [M-H]⁺

4-((4-(4-(4-azido-2,3,5,6-tetrafluoro-N-(pent-4-yn-1-yl)benzamido)butanamido)butyl)amino)-N2,N6-di(quinolin-3-yl)pyridine-2,6-dicarboxamide
Mp	dec. > 105 °C
¹H NMR (300 MHz, DMSO-d₆)	δ (ppm): 11.28 (s, 2H), 9.35 (m, 2H), 8.96 (m, 2H), 8.04 (d, J = 8.8 Hz, 2H), 7.93 – 7.79 (m, 1H), 7.76 - 7.46 (m, 7H), 3.54 - 3.41 (m, 2H), 3.27 – 2.98 (m, 6H), 2.85 – 2.68 (m, 1H), 2.22 – 1.94 (m, 4H), 1.84 – 1.72 (m, 2H), 1.70 - 1.44 (m, 6H)
¹³C NMR (75 MHz, DMSO-d₆)	δ (ppm): 171.31, 171.04, 163.19, 157.92, 156.31, 146.10, 144.67, 143.39, 142.08, 140.28, 138.79, 131.99, 128.71, 127.91, 127.77, 127.22, 124.14, 83.57, 82.96, 71.71, 47.75, 46.80, 44.20, 43.79, 41.79, 38.16, 32.54, 31.50, 26.84, 25.88, 25.63, 24.12, 23.17,15.33, 14.67
LC/MS (Method A)	Retention time 6.97 min, m/z (ESI+) = 874.6 [M-H]⁺

4-((4-(4-(4-benzoyl-N-(pent-4-yn-1-yl)benzamido)butanamido)butyl)amino)-N2,N6-di(quinolin-3-yl)pyridine-2,6-dicarboxamide
Mp	dec. > 105 °C
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 10.29 – 10.14 (m, 2H), 9.16 – 9.09 (m, 2H), 8.87 – 9.08 (m, 2H), 8.06 (d, J = 8.1 Hz, 4H), 7.81 – 7.61 (m, 8H), 7.59 – 7.48 (m, 3H), 7.46 – 7.33 (m, 5H), 7.17 – 7.07 (m, 1H), 5.79 (m, 1H), 3.61 – 3.49 (m, 2H), 3.42 – 3.2 (m, 6H), 2.35 – 2.24 (m, 2H), 2.08 – 1.94 (m, 4H), 1.83 – 1.76 (m, 5H), 1.33 – 1.22 (m, 2H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 196.02, 172.90, 171.77, 163.46, 156.02, 148.79, 145.00, 144.76, 139.78, 138.35, 136.91, 132.97, 131.60, 130.17, 128.51, 128.14, 127.85, 127.33, 126.25, 124.81, 82.23, 69.70, 48.11, 44.47, 42.59, 39.21, 33.69, 27.26, 26.07, 23.64, 15.73
LC/MS (Method A)	Retention time 6.72 min, m/z (ESI+) = 865.6 [M-H]⁺

4-((14-oxo-10-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoyl)-4,7-dioxa-10,15-diazanonadec-1-yn-19-yl)amino)-N2,N6-di(quinolin-3-yl)pyridine-2,6-dicarboxamide
Mp	dec. > 98 °C
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 10.19 (s, 2H), 9.11 (d, J = 2.57 Hz, 2H), 8.85 (s, 2H), 8.07 (d, J = 7.8 Hz, 2H), 7.79 (d, J = 7.7 Hz, 2H), 7.65 (t, J = 7.3 Hz, 2H), 7.54 (t, J = 7.1 Hz, 2H), 7.42 - 7.29 (d, J = 8.1 Hz, 2H), 7.06 (d, J = 7.9 Hz, 2H), 5.83 (bs, 1H), 4.16 - 4.10 (m, 2H) 3.68 – 3.21 (m, 14H), 2.44 (m, 1H), 2.29 - 1.94 (m, 8H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 172.93, 172.11, 163.28, 156.07, 148.89, 144.95, 144.89, 137.41, 131.53, 130.25, 128.70, 128.22, 127.90, 127.42, 126.47, 124.64, 123.81, 120.16, 79.49, 74.94, 70.37, 69.10, 68.34, 58.46, 48.95, 44.78, 42.69, 39.19, 33.73, 29.84, 28.61, 28.07, 27.22, 26.03, 23.60
LC/MS (Method A)	Retention time 6.97 min, m/z (ESI+) = 929.0 [M-H]⁺

4-((10-(4-azido-2,3,5,6-tetrafluorobenzoyl)-14-oxo-4,7-dioxa-10,15-diazanonadec-1-yn-19-yl)amino)-N2,N6-di(quinolin-3-yl)pyridine-2,6-dicarboxamide
Mp	dec. > 114 °C
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 10.20 – 10.08 (m, 2H), 9.09 (s, 2H), 8.86 (s, 2H), 8.06 (d, J = 8.6 Hz, 2H), 7.81 (d, J = 7.8 Hz, 2H), 7.70 – 7.62 (m, 2H), 7.58 – 7.48 (m, 2H), 7.44 (s, 1H), 6.76 (bs, 1H), 5.70 (bs, 1H), 4.17 – 4.03 (m, 2H), 3.67- 3.28 (m, 15H), 2.46 – 2.36 (m, 1H), 2.29 – 2.13 (m, 2H), 2.1 (m, 2H), 2.09 – 1.87 (m, 2H), 1.50 – 1.40 (m, 2H), 1.27 – 1.18 (m, 2H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 172.64, 172.00, 163.20, 160.44, 156.15, 150.21, 148.90, 144.92, 144.69, 144.09, 142.03, 140.69, 138.88, 135.51, 131.48, 128.69, 128.21, 128.17, 127.87, 127.46, 124.51, 121.31, 120.28, 111.47, 79.44, 74.75, 70.52, 70.26, 69.06, 68.26, 66.00, 64.12, 58.43, 58.38, 48.74, 45.19, 42.68, 39.17, 33.33, 29.84, 27.19, 25.92, 23.45
LC/MS (Method A)	Retention time 6.82 min, m/z (ESI+) = 934.0 [M-H]⁺

4-((10-(4-benzoylbenzoyl)-14-oxo-4,7-dioxa-10,15-diazanonadec-1-yn-19-yl)amino)-N2,N6-di(quinolin-3-yl)pyridine-2,6-dicarboxamide
Mp	dec. > 90 °C
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 10.30 - 10.13 (m, 2H), 9.17 – 9.05 (m, 2H), 8.86 -8.78 (m, 2H), 8.05 (d, J = 8.3 Hz, 2H), 7.81 – 7.60 (m, 8H), 7.56 – 7.48 (m, 3H), 7.45 – 7.35 (m, 5H), 7.23 – 7.17 (m, 1H), 5.86 – 5.68 (m, 1H), 4.22 – 4.05 (m, 2H), 3.68 – 3.20 (m, 14H), 2.46 – 2.36 (m, 1H), 2.35 – 2.23 (m, 2H), 2.07 – 1.93 (m, 2H), 1.80 – 1.70 (m, 4H)
¹³C NMR (75 MHz, DMSO-d₆)	δ (ppm): 195.32, 172.39, 171.58, 171.01, 170.12, 169.85, 163.17, 156.29, 146.11, 144.67, 141.00, 140.72, 137.07, 136.79, 132.89, 131.98, 129.69, 128.71, 128.64, 128.35, 127.92, 127.77, 127.21, 127.03, 126.47, 124.14, 80.30, 77.15, 69.49, 68.48, 67.58, 59.18, 58.90, 57.55, 53.61, 48.74, 48.31, 48.12, 43.87, 41.75, 38.13, 32.86, 32.22, 31.34, 29.06, 28.76, 26.83, 25.64, 23.26, 22.14
LC/MS (Method A)	Retention time 6.59 min, m/z (ESI+) = 925.0 [M-H]⁺

4-((17-oxo-13-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoyl)-4,7,10-trioxa-13,18-diazadocos-1-yn-22-yl)amino)-N2,N6-di(quinolin-3-yl)pyridine-2,6-dicarboxamide
Mp	dec. > 75 °C
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 10.28 (s, 2H), 9.11 (s, 2H), 8.81 (s, 2H), 8.03 (d, J = 8.4 Hz, 2H), 7.73 (d, J = 7.9 Hz, 2H), 7.63 (t, J = 7.4 Hz, 2H), 7.51 (t, J = 7.4 Hz, 2H), 7.37 – 7.27 (m, 4H), 7.03 (d, J = 8.0 Hz, 2H), 5.97 – 5.80 (m, 1H), 4.14 (d, J = 2.2 Hz, 2H), 3.72 – 3.09 (m, 20H), 2.42 (t, J = 2.2 Hz, 1H), 2.26 (t, J = 6.3 Hz, 1H), 2.02 – 1.88 (m, 2H), 1.77 – 1.56 (m, 4H)
¹³C NMR (75 MHz, DMSO-d₆)	δ (ppm): 171.54, 170.96, 169.75, 169.45, 163.15, 156.26, 150.84, 146.07, 144.64, 138.90, 138.60, 131.95, 128.68, 128.31, 127.88, 127.74, 127.32, 127.17, 126.40, 126.30, 124.10, 123.61, 120.59, 119.97, 80.26, 77.10, 69.69, 69.50, 68.50, 67.49, 57.48, 48.72, 48.13, 43.85, 41.74, 38.07, 32.81, 32.06, 28.27, 27.74, 26.77, 25.60, 24.13, 23.19
LC/MS (Method A)	Retention time 7.15 min, m/z (ESI+) = 973.5 [M-H]⁺

4-((13-(4-azido-2,3,5,6-tetrafluorobenzoyl)-17-oxo-4,7,10-trioxa-13,18-diazadocos-1-yn-22-yl)amino)-N2,N6-di(quinolin-3-yl)pyridine-2,6-dicarboxamide
Mp	dec. > 58 °C
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 10.34 (s, 2H), 9.08 (s, 2H), 8.71 (s, 2H), 7.99 – 7.89 (m, 2H), 7.70 – 7.51 (m, 4H), 7.49 -7.39 (m, 2H), 7.36 – 7.29 (m, 1H), 7.19 – 6.59 (m, 1H), 6.10 – 5.91 (m, 1H), 4.11 (dd, J = 6.6, 2.3 Hz, 2H), 3.62 – 3.04 (m, 20H), 2.44 – 2.35 (m, 1H), 2.18 - 2.11 (m, 1H), 1.91 – 1.85 (m, 1H), 1.56 – 1.13 (m, 4H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 172.67, 172.09, 163.28, 160.33, 159.56, 156.13, 148.85, 144.94, 144.89, 144.13, 142.12, 140.82, 138.83, 131.51, 128.64, 128.15, 127.83, 127.35, 124.50, 121.16, 111.51, 79.63, 74.86, 74.73, 70.63, 70.48, 70.36, 70.21, 69.11, 69.05, 68.17, 58.42, 53.57, 48.72, 45.11, 42.65, 39.18, 33.27, 27.17, 26.01, 23.38
LC/MS (Method A)	Retention time 7.16 min, m/z (ESI+) = 978.5 [M-H]⁺

4-((13-(4-benzoylbenzoyl)-17-oxo-4,7,10-trioxa-13,18-diazadocos-1-yn-22-yl)amino)-N2,N6-di(quinolin-3-yl)pyridine-2,6-dicarboxamide
Mp	dec. > 65 °C
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 10.40 – 10.26 (m, 2H), 9.11 (s, 2H), 8.75 (s, 2H), 8.00 (d, J = 8.3 Hz, 2H), 7.73 – 7.29 (m, 18H), 5.97 – 5.88 (m, 1H), 4.14 – 4.08 (m, 2H), 3.66 – 3.15 (m, 18H), 2.40 (t, J = 2.3 Hz, 1H), 2.28 (t, J = 6.3 Hz, 1H), 2.03 – 1.92 (m, 3H), 1.73 – 1.48 (m, 4H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 196.07, 172.93, 172.20, 163.38, 156.13, 148.92, 145.14, 145.11, 140.02, 138.19, 137.05, 132.86, 131.56, 130.14, 128.82, 128.49, 128.16, 127.84, 127.29, 126.77, 124.61, 100.12, 79.66, 74.87, 70.62, 70.54, 70.44, 70.33, 69.12, 68.55, 58.45, 48.92, 44.87, 42.67, 39.18, 33.72, 27.20, 26.10, 23.60
LC/MS (Method A)	Retention time 6.79 min, m/z (ESI+) = 969.6 [M-H]⁺

PDC-4,1-N2
Mp	dec. > 175 °C
¹H NMR (300 MHz, DMSO-d₆)	δ (ppm): 11.70 (s,2H), 10.16 (s, 2H), 9.65 (s, 2H), 8.54 ( t, J = 8.57 Hz, 4H), 8.21 (t, J = 8.62 Hz, 2H), 8.05 (t, J = 7.66 Hz, 2H), 7.93 - 7.64 (m, 1H), 7.60 - 7.48 (m, 4H), 7.42 - 7.27 (m, 3H), 4.78 (s, 6H), 3.24 - 2.97 (m, 6H), 2.59 - 2.54 (m, 1H), 2.19 - 2.09 (m, 1H), 1.98 - 1.73 (m, 4H), 1.66 - 1.44 (m, 5H)
¹³C NMR (75 MHz, DMSO-d₆)	δ (ppm): 171.45, 169.07, 163.17, 156.50, 144.68, 137.59, 135.61, 134.00, 133.90, 132.34, 130.30, 129.84, 129.19, 128.57, 127.49, 126.58, 123.58, 119.94, 119.19, 79.53, 49.53, 46.19, 41.76, 38.04, 34.36, 33.51, 32.85, 28.27, 27.74, 26.74, 26.19, 25.49, 23.72
LC/MS (Method A)	Retention time 5.09 min, m/z (ESI+) = 870.0 [M-2I]⁺
UHPLC (Method B)	Retention time 6.59 min
HRMS (ESI, m/z)	calcd for formula C₄₇H₄₅F₃IN₁₀O₄⁺ [M-I]⁺ = 997.2622; found 997.2596

PDC-4,1-N3
Mp	dec. > 165 °C
¹H NMR (300 MHz, DMSO-d₆)	δ (ppm): δ 11.73 (s, 2H), 10.11 (s, 2H), 9.64 (s, 2H), 8.56 (d, J = 8.6 Hz, 4H), 8.25 (t, J = 7.7 Hz, 2H), 8.09 (t, J = 7.6 Hz, 2H), 7.99 – 7.79 (m, 1H), 7.75 – 7.43 (m, 3H), 4.79 (s, 6H), 4.34 (s, 1H), 4.14 (s, 1H), 3.61 – 3.50 (m, 1H), 3.19 – 2.97 (m, 3H), 2.74 (s, 1H), 2.19 – 2.09 (m, 1H), 2.05 – 1.94 (m, 1H), 1.93 – 1.41 (m, 7H), 1.28 – 1.15 (m, 1H)
¹³C NMR (75 MHz, DMSO-d₆)	δ (ppm): 171.26, 171.05, 163.20, 163.11, 158.06, 157.91, 156.54, 144.80, 143.57, 142.06, 140.31, 138.55, 135.67, 134.09, 133.93, 132.37, 130.34, 129.87, 129.22, 119.23, 78.82, 78.35, 56.03, 47.65, 46.19, 44.98, 41.76, 38.10, 33.89, 32.56, 31.38, 26.71, 25.50, 23.75, 23.00
LC/MS (Method A)	Retention time 4.24 min, m/z (ESI+) = 875.0 [M-2I]⁺
UHPLC (Method B)	Retention time 6.44 and 6.59 min (two rotamers)
HRMS (ESI, m/z)	calcd for formula C₄₅H₄₁F₄IN₁₁O₄⁺ [M-I]⁺ = 1002.2324; found 1002.2365

PDC-4,1-Bp
Mp	dec. > 137 °C
¹H NMR (300 MHz, DMSO-d₆)	δ (ppm): 11.71 (s, 2H), 10.13 (s, 2H), 9.64 (s, 2H), 8.56 (d, J = 8.7 Hz, 4H), 8.23 (m, 2H), 8.07 (m, 2H), 7.81 – 7.52 (m, 12H), 4.78 (s, 6H), 4.31 (bs, 1H), 4.05 (bs, 1H), 3.51 (bs, 1H), 3.20 - 2.92 (m, 4H), 2.17 (bs, 1H), 2.06 - 1.72 (m, 4H), 1.70 – 1.33 (m, 5H)
¹³C NMR (75 MHz, DMSO-d₆)	δ (ppm): 195.26, 171.47, 170.95, 169.41, 163.19, 156.52, 144.71, 139.61, 137.81, 137.57, 136.62, 135.67, 134.10, 133.93, 132.97, 132.37, 130.34, 129.86, 129.76, 129.70, 129.22, 128.64, 126.61, 119.23, 79.56, 46.18, 41.75, 38.05, 26.72, 25.50
LC/MS (Method A)	Retention time 5.25 min, m/z (ESI+) = 865.5 [M-2I-H]⁺
UHPLC (Method B)	Retention time 6.08 min
HRMS (ESI, m/z)	calcd. for formula C₅₂H₅₀IN₈O₅⁺ [M-I]⁺ = 993.2949; found = 993.2979

PDC-4,3-N2
Mp	dec. > 148 °C
¹H NMR (300 MHz, DMSO-d₆)	δ (ppm): 11.70 (s, 2H), 10.17 (s, 2H), 9.66 (s, 2H), 8.55 (t, J = 9.03 Hz, 4H), 8.21 (t, J = 7.98 Hz, 2H), 8.06 (t, J = 7.79 Hz, 2H), 7.96 – 7.55 (m, 4H), 7.51 (d, J = 8.53 Hz, 2H), 7.32 (bs, 2H), 4.79 (s, 6H), 3.46 (m, 1H), 3.30 - 2.96 (m, 7H), 2.57 (m, 1H), 2.23 – 2.16 (m, 2H), 2.02 (m, 2H), 1.85 – 1.46 (m, 8H)
¹³C NMR (75 MHz, DMSO-d₆)	δ (ppm): 171.55, 170.97, 169.39, 163.18, 156.52, 144.70, 138.71, 135.63, 134.01, 133.92, 132.35, 130.32, 129.86, 129.21, 128.14, 127.39, 126.51, 123.63, 119.99, 119.20, 83.93, 83.15, 71.52, 71.39, 48.18, 47.49, 46.22, 43.88, 41.80, 38.07, 34.44, 32.89, 32.08, 28.30, 27.77, 26.85, 26.21, 25.53, 24.13, 23.35, 15.59, 15.01
LC/MS (Method A)	Retention time 5.25 min, m/z (ESI+) = 898.0 [M-2I]⁺
UHPLC (Method B)	Retention time 6.68 min
HRMS (ESI, m/z)	calcd for formula C₄₉H₄₉F₃IN₁₀O₄⁺ [M-I]⁺ = 1025.2935; found 1025.2965

PDC-4,3-N3
Mp	dec. > 114 °C
¹H NMR (300 MHz, DMSO-d₆)	δ (ppm): 11.71 (s, 2H), 10.13 (s, 2H), 9.65 (s, 2H), 8.59 - 8.48 (m, 4H), 8.23 (t, J = 8.2 Hz, 2H), 8.07 (t, J = 7.6 Hz, 2H), 7.94 - 7.79 (m, 1H), 7.75 – 7.45 (m, 3H), 4.79 (s, 6H), 3.53 - 3.43 (m, 2H), 3.27 - 2.99 (m, 6H), 2.84 – 2.70 (m, 1H), 2.22 - 1.95 (m, 4H), 1.84 - 1.73 (m, 2H), 1.67 - 1.48 (m, 6H)
¹³C NMR (75 MHz, DMSO-d₆)	δ (ppm): 171.31, 171.05, 163.23, 157.91, 156.57, 144.74, 143.50, 142.09, 140.30, 138.55, 135.70, 134.14, 133.96, 132.40, 130.37, 129.89, 129.25, 119.25, 83.56, 82.95, 71.67, 47.71, 46.82, 46.20, 44.19, 43.78, 41.80, 38.04, 34.68, 32.54, 31.49, 26.85, 25.87, 25.52, 23.16, 15.32, 14.66
LC/MS (Method A)	Retention time 5.26 min, m/z (ESI+) = 902.5 [M-2I-H]⁺
UHPLC (Method B)	Retention time 6.61 min (two rotamers)
HRMS (ESI, m/z)	calcd. for formula C₄₇H₄₅IN₁₁O₄F₄⁺ [M-I]⁺ = 1130.2637; found = 1130.2666

PDC-4,3-Bp
Mp	dec. > 152 °C
¹H NMR (300 MHz, DMSO-d₆)	δ (ppm) : 11.71 (s, 2H), 10.12 (s, 2H), 9.64 (s, 2H), 8.62 - 8.45 (m, 4H), 8.26 -8.04 (m, 5H), 7.95 (bs, 1H), 7.79 - 7.50 (m, 10H), 4.78 (s, 6H), 3.84 - 3.69 (m, 3H), 3.50 - 3.35 (m, 3H), 3.14 - 2.97 (m, 2H), 2.30 -2.11 (m, 3H), 2.05 - 1.90 (m, 2H), 1.83 - 1.44 (m, 8H)
¹³C NMR (75 MHz, DMSO-d₆)	δ (ppm): 195.18, 171.43, 170.84, 169.90, 163.09, 156.34, 144.70, 140.66, 137.03, 136.61, 135.45, 133.88, 133.76, 132.78, 132.25, 130.17, 129.74, 129.62, 129.54, 129.06, 128.51, 126.38, 119.04, 71.43, 46.02, 41.65, 37.95, 34.30, 26.68, 26.08, 25.40, 15.48, 14.95
LC/MS (Method A)	Retention time 5.02 min, m/z (ESI+) = 894.0 [M-2I]⁺
UHPLC (Method B)	Retention time 6.29 min
HRMS (ESI, m/z)	calcd. for formula C₅₄H₅₄IN₈O₅⁺ [M-I]⁺ = 1021.3262; found = 1021.3299

PDC-4,DEG-N2
Mp	dec. > 105 °C
¹H NMR (300 MHz, DMSO-d₆)	δ (ppm): 11.72 (s, 2H), 10.10 (s, 2H), 9.63 (s, 2H), 8.57 (d, J = 10.1 Hz , 4H), 8.24 (t, J = 8.0 Hz, 2H), 8.09 (t, J = 7.6 Hz, 2H), 7.90 (bs, 1H), 7.77-7.44 (m, 5H), 7.31 (d, J = 7.9 Hz, 2H), 4.78 (s, 6H), 4.13 (s, 2H), 3.64 - 3.38 (m, 10H), 3.28 (bs, 3H), 3.14 (bs, 2H), 3.01 (bs, 1H), 2.14 (bs, 1H), 1.96 - 1.41 (m, 8H)
¹³C NMR (75 MHz, DMSO-d₆)	δ (ppm): 171.58, 171.01, 169.79, 169.49, 163.21, 156.55, 144.73, 138.91, 138.61, 135.68, 134.09, 133.94, 132.37, 130.35, 129.88, 129.23, 128.14, 128.00, 127.89, 127.35, 126.44, 126.33, 123.63, 119.99, 119.24, 116.35, 80.27, 77.15, 69.45, 68.48, 67.64, 67.46, 57.54, 48.16, 46.21, 43.85, 41.79, 38.06, 34.42, 32.84, 28.30, 27.76, 26.81, 25.52, 24.08, 23.21
LC/MS (Method A)	Retention time 5.26 min, m/z (ESI+) = 957.7 [M-2I-H]⁺
UHPLC (Method B)	Retention time 6.60 min
HRMS (ESI, m/z)	calcd. for formula C₅₁H₅₃F₃IN₁₀O₆⁺ [M-I]⁺ = 1085.3146; found = 1085.3181

PDC-4,DEG-N3
Mp	dec. > 182 °C
¹H NMR (300 MHz, DMSO-d₆)	δ (ppm): 11.75 (bs, 2H), 10.10 (s, 2H), 9.63 (s, 2H), 8.62 – 8.46 (m, 4H), 8.28 - 8.17 (m, 2H), 8.12 – 8.02 (m, 2H), 7.94 – 7.79 (m, 1H), 7.77 – 7.42 (m, 3H), 4.78 (s, 6H), 4.12 (d, J = 16.0 Hz, 2H), 3.72 – 3.39 (m, 9H), 3.18 - 2.93 (m, 3H), 2.18 – 2.07 (m, 2H), 2.04 – 1.91 (m, 2H), 1.87 – 1.74 (m, 2H), 1.71– 1.42 (m, 5H)
¹³C NMR (75 MHz, DMSO-d₆)	δ (ppm): 171.36, 171.08, 163.23, 156.57, 144.74, 135.72, 134.16, 133.97, 132.42, 130.40, 129.88, 129.25, 119.27, 69.48, 68.34, 67.60, 57.50, 48.41, 46.16, 44.33, 41.74, 38.03, 32.51, 26.79, 25.48
LC/MS (Method A)	Retention time 5.20 min, m/z (ESI+) = 963.0 [M-2I]⁺
UHPLC (Method B)	Retention time 6.54 min (two rotamers)
HRMS (ESI, m/z)	calcd. for formula C₄₉H₄₉F₄IN₁₁O₆⁺ [M-I]⁺ = 1090.2848; found = 1090.3000

PDC-4,DEG-Bp
Mp	dec. > 130 °C
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 11.49 – 11.22 (m, 4H), 9.81 (s, 2H), 8.11 (t, J = 9.5 Hz, 3H), 7.97 (t, J = 7.8 Hz, 2H), 7.90 – 7.75 (m, 6H), 7.60 – 7.41 (m, 5H), 7.37 – 7.30 (m, 2H), 6.99 (bs, 1H), 6.15 (bs, 1H), 4.81 (s, 6H), 4.21 – 4.13 (m, 2H), 3.80 – 3.11 (m, 15H), 2.50 – 2.39 (m, 1H), 2.37 – 2.31 (m, 1H), 2.08 - 1.97 (m, 2H), 1.82 – 1.72 (m, 2H), 1.38 – 1.27 (m, 2H)
¹³C NMR (75 MHz, DMSO-d₆)	δ (ppm): 195.29, 171.58, 171.01, 170.11, 163.22, 156.56, 144.74, 140.96, 140.69, 137.16, 136.74, 135.71, 134.15, 133.95, 132.90, 132.41, 130.38, 129.88, 129.66, 129.24, 128.63, 127.00, 126.44, 119.26, 77.17, 69.47, 68.47, 67.59, 57.54, 48.07, 46.17, 43.85, 41.76, 38.05, 32.82, 26.82, 25.51
LC/MS (Method A)	Retention time 5.03 min, m/z (ESI+) = 954.0 [M-2I]⁺
UHPLC (Method B)	Retention time 6.21 min
HRMS (ESI, m/z)	calcd. for formula C₅₆H₅₈IN₈O₇⁺ [M-I]⁺ = 1081.3473; found = 1081.3521

PDC-4,TEG-N2
Mp	dec. > 122 °C
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 11.49 -11.32 (m, 2H), 11.23 (s, 2H), 9.84 (s, 2H), 8.20 – 8.05 (m, 4H), 8.02 – 7.90 (m, 2H), 7.88 – 7.76 (m, 2H), 7.55 – 7.38 (m, 2H), 7.35 – 7.29 (m, 1H), 7.24 – 7.19 (m, 2H), 6.98 (m, 1H), 6.16 (m, 1H), 4.80 (s, 6H), 4.19 (d, J = 2.0 Hz, 2H), 3.76 – 3.50 (m, 14H), 3.46 – 3.13 (m, 7H), 2.46 (s, 1H), 2.37 – 2.27 (m, 1H), 2.06 – 1.94 (m, 2H), 1.85 – 1.74 (m, 2H)
¹³C NMR (75 MHz, DMSO-d₆)	δ (ppm): 171.61, 171.02, 169.79, 169.47, 163.21, 156.56, 144.75, 138.92, 138.62, 135.68, 134.09, 133.95, 132.38, 130.36, 129.88, 129.24, 128.16, 128.00, 127.88, 127.37, 126.35, 123.64, 119.99, 119.25, 80.28, 77.15, 69.73, 69.52, 68.53, 67.57, 57.51, 48.69, 48.17, 46.21, 43.88, 41.79, 38.07, 32.84, 32.12, 28.84, 28.30, 27.77, 27.24, 26.79, 26.21, 25.53, 24.10, 23.21
LC/MS (Method A)	Retention time 7.06 min, m/z (ESI+) = 973.7 [M-2I-N₂]⁺
UHPLC (Method B)	Retention time 6.64 min
HRMS (ESI, m/z)	calcd. for formula C₅₃H₅₇IN₁₀O₇F₃⁺ [M-I]⁺ = 1129.3409; found = 1129.3411

PDC-4,TEG-N3
Mp	dec. > 142 °C
¹H NMR (300 MHz, DMSO-d₆)	δ (ppm): 11.72 (s, 2H), 10.10 (s, 2H), 9.63 (s, 2H), 8.59 – 8.50 (m, 4H), 8.24 (t, J = 7.8 Hz, 2H), 8.08 (t, J = 7.7 Hz, 2H), 7.94 - 7.78 (m, 1H), 7.74 – 7.48 (m, 3H), 4.78 (s, 6H), 4.12 (m, 2H), 3.63 – 3.35 (m, 14H), 3.31 – 2.97 (m, 6H), 2.17 – 2.06 (m, 1H), 2.02 – 1.91 (m, 1H), 1.86 – 1.74 (m, 1H), 1.66 - 1.46 (m, 4H)
¹³C NMR (75 MHz, DMSO-d₆)	δ (ppm): 171.39, 171.12, 163.23, 158.35, 158.10, 157.87, 157.60, 156.57, 144.73, 143.45, 141.90, 140.25, 138.64, 135.71, 134.14, 133.96, 132.41, 132.37, 130.38, 129.88, 129.25, 119.26, 80.27, 77.12, 69.81, 69.72, 69.61, 69.51, 68.52, 68.46, 67.65, 67.49, 57.50, 48.39, 48.00, 46.20, 44.50, 44.34, 41.80, 38.09, 32.55, 31.52, 26.80, 25.52, 24.04, 23.07
LC/MS (Method A)	Retention time 5.36 min, m/z (ESI+) = 1006.7 [M-2I-H]⁺
UHPLC (Method B)	Retention time 6.58 min (two rotamers)
HRMS (ESI, m/z)	calcd. for formula C₅₁H₅₃F₄IN₁₁O₇⁺ [M-I]⁺ = 1134.3110; found = 1134.3121

PDC-4,TEG-Bp
Mp	dec. > 117 °C
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 11.44 – 11.35 (m, 2H), 11.26 (s, 2H), 9.81 (s, 2H), 8.16 – 8.05 (m, 4H), 7.96 (t, J = 7.9 Hz, 2H), 7.89 – 7.76 (m, 6H), 7.60 – 7.43 (m, 5H), 7.35 – 7.31 (m, 1H), 7.00 (s, 1H), 6.18 (s, 1H), 4.80 (s, 6H), 4.19 – 4.13 (m, 2H), 3.80 – 3.44 (m, 15H), 3.41 – 3.07 (m, 5H), 2.44 (m, 1H), 2.40 – 2.29 (m, 1H), 2.11 – 1.97 (m, 1H), 2.12 – 1.97 (m, 2H), 1.83 - 1.71 (m, 3H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 196.21, 172.84, 171.98, 171.09, 162.89, 156.04, 147.18, 146.15, 140.70, 140.51, 138.24, 138.15, 137.20, 134.72, 133.55, 132.93, 132.70, 132.43, 130.39, 130.20, 130.04, 129.52, 128.59, 127.06, 126.72, 117.67, 79.68, 74.98, 70.72, 70.66, 70.54, 70.48, 69.19, 68.69, 58.52, 45.71, 44.81, 42.77, 39.10, 33.69, 27.17, 25.88, 25.83, 25.79, 23.65, 23.59, 23.58
LC/MS (Method A)	Retention time 5.33 min, m/z (ESI+) = 997.6 [M-2I-H]⁺
UHPLC (Method B)	Retention time 6.23 min
HRMS (ESI, m/z)	calcd. for formula C₅₈H₆₂IN₈O₈⁺ [M-I]⁺ = 1125.3735; found = 1125.3689

3-(3-(but-3-yn-1-yl)-3H-diazirin-3-yl)-N-methylpropanamide
Mp	59 – 60 °C
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 5.41 (bs, 1H), 2.81 (d, J = 4.86 Hz, 3H), 2.05 – 1.97 (m, 3H), 1.96 – 1.81 (m, 4H), 1.65 (t, J = 7.24 Hz, 2H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 172.06, 82.83, 69.32, 32.51, 30.26, 28.61, 27.96, 26.61, 13.41

4-benzoyl-N,N-diethylbenzamide
Mp	78 – 79 °C
¹H NMR (300 MHz, CDCl₃)	δ (ppm): 7.81 (t, J = 7.5 Hz, 4H), 7.60 (t, J = 7.4 Hz, 1H), 7.49 (t, J = 7.6 Hz, 4H), 3.57 (d, J = 6.7 Hz, 2H), 3.25 (d, J = 6.6 Hz, 2H), 1.30 - 1.20 (m, 3H), 1.16 – 1.07 (m, 3H)
¹³C NMR (75 MHz, CDCl₃)	δ (ppm): 196.26, 170.37, 141.13, 138.22, 137.27, 132.86, 130.29, 130.20, 128.52, 126.33, 43.37, 39.43, 14.36, 13.02
LC/MS	Retention time 6.22 min, m/z (ESI+) = 282.19
HRMS (ESI, m/z)	calcd. for formula C₁₈H₂₀NO₂⁺ [M+H]⁺ = 282.1494; found = 282.1503

4-benzoyl-N,N-diethylbenzamide
Laser flash photolysis	Bp-CONEt2 generates a reactive excited state with an extremely short lifetime (τ½ < 50 ns) that is insensitive to oxygen (Figure S48)

Bp-CONEt2 + dT photoreaction
HPLC (260 nm), reaction mixture after irradiation	A mixture of six primary chromatographic peaks; the product distribution remained unchanged in the presence of oxygen
¹H NMR, photoadduct mixture	A mixture of eight oxetanes formed via a [2+2] Paternò–Büchi photocycloaddition; 71 % N,O-acetals (regioisomers #1–#4) and 29 % substituted oxetanes (#5–#8)
HPLC (260 nm), after 2 h at 95 °C	N,O-acetal #2 reverted to the starting materials, whereas oxetane #6 remained stable

N,N-diethyl-4-((1S,6R,8S)-2-((2R,4S,5R)-4-hydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)-6-methyl-3,5-dioxo-8-phenyl-7-oxa-2,4-diazabicyclo[4.2.0]octan-8-yl)benzamide
¹H NMR (700 MHz, MeOD-d₄)	δ (ppm): 7.74 (d, J = 8.37 Hz, 2H), 7.58 (d, J = 7.31 Hz, 2H), 7.43 (d, J = 8.37 Hz, 2H), 7.29 (t, J = 7.79 Hz, 2H), 7.22 (t, J = 7.36 Hz, 1H), 6.28 (dd, J = 7.58, 6.30 Hz, 1H), 5.99 (s, 1H), 4.49 (dt, J = 6.57, 3.50 Hz, 1H), 3.84 (q, J = 3.55 Hz, 1H), 3.73 (ddd, J = 27.38, 11.98, 3.46 Hz, 2H), 3.54 (q, J = 7.42 Hz, 2H), 3.26 (q, J = 7.24 Hz, 2H), 2.53 (ddd, J = 13.78, 7.63, 6.30 Hz, 1H), 2.29 (ddd, J = 13.56, 6.25, 3.60 Hz, 1H), 1.38 (s, 3H), 1.24 (t, J = 6.52 Hz, 3H), 1.11 (t, J = 6.62 Hz, 3H)
¹³C NMR (176 MHz, MeOD-d₄)	δ (ppm): 173.2, 171.8, 153.0, 144.2, 143.2, 137.3, 128.9, 128.7, 127.4, 127.3, 126.7, 90.0, 87.7, 85.2, 83.8, 72.2, 63.0, 55.5, 45.0, 40.9, 40.4, 19.5, 14.3, 13.0

N,N-diethyl-4-((1S,6R,8R)-2-((2R,4S,5R)-4-hydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)-6-methyl-3,5-dioxo-8-phenyl-7-oxa-2,4-diazabicyclo[4.2.0]octan-8-yl)benzamide
¹H NMR (700 MHz, MeOD-d₄)	δ (ppm): 7.68 (d, J = 8.58 Hz, 2H), 7.64 (d, J = 7.42 Hz, 2H), 7.42 (t, J = 7.84 Hz, 2H), 7.31 (dt, J = 6.78, 2.01 Hz, 3H), 6.28 (dd, J = 7.63, 6.36 Hz, 1H), 5.96 (s, 1H), 4.48 (dt, J = 6.57, 3.50 Hz, 1H), 3.84 (q, J = 3.60 Hz, 1H), 3.71 (ddd, J = 28.25, 11.94, 3.55 Hz, 2H), 3.52 (q, J = 6.78 Hz, 2H), 3.23 (q, J = 7.08 Hz, 2H), 2.52 (ddd, J = 13.78, 7.63, 6.25 Hz, 1H), 2.29 (ddd, J = 13.56, 6.15, 3.50 Hz, 1H), 1.38 (s, 3H), 1.22 (t, J = 6.62 Hz, 3H), 1.09 (t, J = 6.57 Hz, 3H)
¹³C NMR (176 MHz, MeOD-d₄)	δ (ppm): 173.2, 171.9, 153.0, 145.2, 142.0, 137.1, 129.5, 128.9, 127.1, 126.9, 126.8, 89.9, 87.7, 85.1, 83.9, 72.2, 63.1, 55.7, 44.9, 40.8, 40.4, 19.5, 14.4, 13.0

N,N-diethyl-4-((1R,6S,8S)-2-((2R,4S,5R)-4-hydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)-6-methyl-3,5-dioxo-8-phenyl-7-oxa-2,4-diazabicyclo[4.2.0]octan-8-yl)benzamide
¹H NMR (700 MHz, MeOD-d₄)	δ (ppm): 7.71 (d, J = 8.48 Hz, 2H), 7.64 (d, J = 7.42 Hz, 2H), 7.42 (t, J = 7.95 Hz, 2H), 7.32 – 7.28 (m, 3H), 6.20 (t, J = 6.94 Hz, 1H), 5.73 (s, 1H), 4.39 (dt, J = 6.78, 3.66 Hz, 1H), 3.92 (q, J = 4.19 Hz, 1H), 3.79 (ddd, J = 21.07, 11.95, 4.24 Hz, 2H), 3.52 (d, J = 7.10 Hz, 2H), 3.23 (d, J = 6.78 Hz, 2H), 2.35 (p, J = 6.68 Hz, 1H), 2.17 (ddd, J = 13.56, 6.68, 3.81 Hz, 1H), 1.40 (s, 3H), 1.22 (t, J = 6.62 Hz, 3H), 1.09 (t, J = 6.62 Hz, 3H)
¹³C NMR (176 MHz, MeOD-d₄)	δ (ppm): 173.2, 171.8, 153.2, 145.1, 142.0, 137.1, 129.5, 128.9, 127.2, 126.9, 126.8, 89.8, 88.2, 86.8, 85.6, 72.6, 63.6, 56.1, 44.9, 40.8, 38.9, 19.2, 14.4, 13.0

N,N-diethyl-4-(2-((2R,4S,5R)-4-hydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)-6-methyl-3,5-dioxo-8-phenyl-7-oxa-2,4-diazabicyclo[4.2.0]octan-8-yl)benzamide
Identifier	#6
Stereochemistry	Unknown
¹H NMR (700 MHz, MeOD-d₄)	δ (ppm): 7.51 (d, J = 8.37, 2H), 7.44 (dd, J = 10.65, 8.11 Hz, 4H), 7.38 (t, J = 7.47 Hz, 2H), 7.34 (dd, J = 8.32, 6.09 Hz, 1H), 6.21 (dd, J = 9.11, 5.93 Hz, 1H), 5.31 (s, 1H), 4.14 (d, J = 6.04 Hz, 1H), 3.79 (q, J = 3.44 Hz, 1H), 3.61 (qd, J = 11.60, 3.50 Hz, 2H), 3.58 – 3.52 (m, 2H), 3.29 (m, 2H), 2.05 (ddd, J = 13.14, 5.93, 2.01 Hz, 1H), 1.82 (ddd, J = 13.10, 9.12, 6.12 Hz, 1H), 1.79 (s, 3H), 1.26 (t, J = 6.94 Hz, 3H), 1.16 (t, J = 6.83 Hz, 3H)
¹³C NMR (176 MHz, MeOD-d₄)	δ (ppm): 173.2, 172.9, 153.5, 143.4, 140.6, 137.8, 129.8, 129.6, 128.4, 127.9, 127.1, 92.5, 87.6, 86.4, 78.4, 73.1, 63.7, 63.6, 45.2, 39.0, 22.3, 14.4, 13.1

N,N-diethyl-4-(2-((2R,4S,5R)-4-hydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)-6-methyl-3,5-dioxo-8-phenyl-7-oxa-2,4-diazabicyclo[4.2.0]octan-8-yl)benzamide
Identifier	#8
Stereochemistry	Unknown
¹H NMR (700 MHz, MeOD-d₄)	δ (ppm): 7.65 (dd, J = 7.74, 5.30 Hz, 4H), 7.39 (t, J = 7.63 Hz, 2H), 7.35 (d, J = 7.35 Hz, 2H), 7.33 (t, J = 7.32 Hz, 1H), 6.18 (dd, J = 8.32, 5.67 Hz, 1H), 5.12 (s, 1H), 4.20 (dt, J = 4.87, 2.23 Hz, 1H), 3.80 (td, J = 4.34, 2.65 Hz, 1H), 3.54 (q, J = 6.76 Hz, 2H), 3.28 (q, J = 7.21 Hz, 2H), 3.12 (ddd, J = 31.36, 11.43, 4.07 Hz, 2H), 2.10 (ddd, J = 13.33, 5.76, 2.19 Hz, 1H), 2.03 (ddd, J = 14.31, 8.31, 5.83 Hz, 1H), 1.78 (s, 3H), 1.24 (t, J = 6.78 Hz, 3H), 1.12 (t, J = 6.73 Hz, 3H)
¹³C NMR (176 MHz, MeOD-d₄)	δ (ppm): 173.3, 172.6, 152.4, 146.5, 139.6, 137.6, 129.2, 129.0, 128.0, 127.9, 127.0, 92.6, 88.6, 86.8, 78.3, 72.9, 63.0, 63.0, 45.0, 40.9, 40.0, 22.5, 14.4, 13.0

4-((1-((2R,4S,5R)-4-hydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)-5-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)oxy)-N-methyloct-7-ynamide
Identifier	#dT1
¹H NMR (700 MHz, CD₃OD)	δ (ppm): 8.09 (d, J = 1.3 Hz, 1H), 6.24 (t, J = 6.4 Hz, 1H), 5.44 (tt, J = 7.5, 4.5 Hz, 1H), 4.41 (dt, J = 6.2, 3.7 Hz, 1H), 3.97 (q, J = 3.5 Hz, 1H), 3.84 (dd, J = 12.1, 3.1 Hz, 1H), 3.75 (dd, J = 12.1, 3.7 Hz, 1H), 2.68 (s, 3H), 2.36 – 2.35 (m, 1H), 2.37 – 2.23 (m, 10H), 2.13 – 2.04 (m, 3H), 1.95 (d, J = 1.2 Hz, 3H)
¹³C NMR (176 MHz, CD₃OD)	δ (ppm): 175.60, 174.95, 156.47, 136.74, 117.60, 89.43, 87.88, 83.91, 79.47, 71.69, 70.26, 62.46, 42.32, 33.59, 32.59, 30.47, 26.34, 15.40, 13.65
HRMS (ESI, m/z)	calcd. for formula C₁₉H₂₇N₃O₆ [M-Na]⁺ = 416.1792; found = 416.1799

4-((1-((2R,4S,5R)-4-hydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)-5-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)oxy)-N-methyloct-7-ynamide
Identifier	#dT2
¹H NMR (700 MHz, CD₃OD)	δ (ppm): 8.07 (d, J = 1.3 Hz, 1H), 6.27 (t, J = 6.5 Hz, 1H), 5.44 (ddd, J = 12.2, 7.2, 4.8 Hz, 1H), 4.41 (dt, J = 6.8, 3.6 Hz, 1H), 3.97 (q, J = 3.4 Hz, 1H), 3.84 – 3.82 (m, 1H), 3.75 (dd, J = 12.1, 3.7 Hz, 1H), 2.69 (s, 3H), 2.38 – 2.36 (m, 1H), 2.35 – 2.25 (m, 7H), 2.10 – 1.96 (m, 3H), 1.95 (d, J = 1.2 Hz, 3H)
¹³C NMR (176 MHz, CD₃OD)	δ (ppm): 175.53, 174.94, 156.56, 136.82, 117.62, 89.46, 87.93, 83.89, 79.52, 71.16, 64.08, 42.16, 34.95, 33.08, 30.78, 30.76, 26.01, 15.35, 14.43
HRMS (ESI, m/z)	calcd. for formula C₁₉H₂₇N₃O₆ [M-Na]⁺ = 416.1792; found = 416.1800

4-((1-((2R,4S,5R)-4-hydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)-5-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)oxy)-N-methyloct-7-ynamide
Identifiers	#dT1 and #dT2
NMR	Minor adducts #dT1 and #dT2 (Figure S42) were characterized as C2O-alkylation products, with two new deshielded protons (Fa and Fb,) at 5.45 and 5.44 ppm and ¹³C NMR signals at ~79 ppm, confirming the formation of a stable C–O bond (Figure S43)

4-(3-((2R,3R,4S,5R)-3,4-dihydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)-5-methyl-2,6-dioxo-3,6-dihydropyrimidin-1(2H)-yl)-N-methyloct-7-ynamide
Identifier	#dT3
¹H NMR (700 MHz, CD₃OD)	δ (ppm): 7.85 – 7.80 (m, 1H), 6.26 (m, 1H), 5.10 (m, 1H), 4.39 (s, 1H), 3.91 (m, 1H), 3.81 (dd, J = 12.0, 3.1 Hz, 1H), 3.74 (dd, J = 12.0, 3.7 Hz, 1H), 2.64 (m, 3H), 2.55 – 2.46 (m, 1H), 2.42 (m, 1H), 2.30 – 2.26 (m, 1H), 2.24 – 2.18 (m, 1H), 2.18 – 2.04 (m, 5H), 1.99 (m, 1H), 1.89 (m, 4H)
¹³C NMR (176 MHz, CD₃OD)	δ (ppm): 175.66, 166.79, 151.71, 136.40, 110.10, 88.82, 86.74, 83.87, 71.94, 69.74, 62.69, 54.40, 41.44, 34.03, 31.28, 28.67, 26.31, 16.77, 13.51
HRMS (ESI, m/z)	calcd. for formula C₁₉H₂₇N₃O₆ [M-Na]⁺ = 416.1792; found = 416.1793
HSQC and HMBC NMR	The major product, dT3, was identified by HSQC and HMBC NMR as a mixture of two diastereoisomers resulting from N3-alkylation (Figures 9 - 10). HMBC correlations between the abstracted proton (Fa and Fb, Figures 9A and Figure 10A) and the thymine carbonyls (C2 and C4, Figures 10C), confirmed the alkylation site (Figure 10B)
Temperature-dependent NMR	Temperature-dependent NMR studies demonstrated that the signal doubling in #dT3 arises from a conformational equilibrium between rotamers that coalesce at 50 °C (Figure 11)
HSQC and HMBC	HSQC and HMBC experiments show that protons Fa and Fb correlate to two different carbons at 54.4 ppm and 56.3 ppm (Figure 10A), which are both carbon chemical shift values characteristic of a C-atom bound to an N-atom
HMBC	The HMBC shows that the Fa proton (5.09 ppm) is coupled to both carbonyl C4 and C2 at 151.7 ppm and 166.8 ppm (Figure 10B), which have been assigned by 3JCH couplings as highlighted in Figure 10B. Fb proton (4.94 ppm) is coupled to the carbonyl C4 at 166.2 ppm, which exhibits a slightly different chemical shift to the carbonyl C4 coupled to the proton Fa

4-(2-amino-9-((2R,4S,5R)-4-hydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)-6-oxo-6,9-dihydro-1H-purin-1-yl)-N-methyloct-7-ynamide
Identifier	#dG1
¹H NMR (700 MHz, CD₃OD)	δ (ppm): 7.95 (s, 1H), 6.26 (dd, J = 7.7, 6.2 Hz, 1H), 4.53 (dt, J = 5.9, 3.0 Hz, 1H), 4.44 (tt, J = 9.2, 5.4 Hz, 1H), 4.00 (q, J = 3.8 Hz, 1H), 3.83 – 3.77 (m, 1H), 3.73 (dd, J = 12.1, 3.9 Hz, 1H), 2.74 – 2.58 (m, 6H), 2.35 (ddd, J = 13.4, 6.2, 3.0 Hz, 1H), 2.20 – 1.99 (m, 7H)
¹³C NMR (176 MHz, CD₃OD)	δ (ppm): 176.01, 159.97, 157.14, 150.16, 138.39, 118.73, 89.38, 85.87, 83.81, 72.86, 70.44, 63.48, 59.31, 52.08, 41.27, 32.60, 31.93, 29.39, 26.32, 16.48
HRMS (ESI, m/z)	calcd. for formula C₁₉H₂₆N₆O₅ [M-H]⁺ = 419.2037; found = 419.2044

4-(2-amino-9-((2R,4S,5R)-4-hydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)-6-oxo-6,9-dihydro-1H-purin-1-yl)-N-methyloct-7-ynamide
Identifier	#dG2
¹H NMR (700 MHz, CD₃OD)	δ (ppm): 7.94 (s, 1H), 6.26 (t, J = 6.9 Hz, 1H), 4.53 (dt, J = 5.9, 3.0 Hz, 1H), 4.44 (tt, J = 9.4, 5.3 Hz, 1H), 3.99 (q, J = 3.5 Hz, 1H), 3.79 (dt, J = 12.0, 4.0 Hz, 1H), 3.73 (tt, J = 6.8, 3.9 Hz, 1H), 2.75 – 2.57 (m, 6H), 2.35 (ddd, J = 13.5, 6.3, 3.2 Hz, 1H), 2.20 – 1.99 (m, 7H)
¹³C NMR (176 MHz, CD₃OD)	δ (ppm): 176.04, 159.99, 157.18, 150.22, 137.19, 114.15, 89.34, 85.70, 83.84, 72.88, 70.43, 63.49, 59.25, 52.05, 41.34, 32.59, 31.99, 29.40, 26.32, 16.49
HRMS (ESI, m/z)	calcd. for formula C₁₉H₂₆N₆O₅ [M-H]⁺ = 419.2037; found = 419.2048

4-(2-amino-9-((2R,4S,5R)-4-hydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)-6-oxo-6,9-dihydro-1H-purin-1-yl)-N-methyloct-7-ynamide
Identifiers	#dG1 and #dG2
NMR	The primary products #dG1 and #dG2 are epimers resulting from N1-alkylation (Figure 13E), and similarly to #dT3, are both a mixture of two different rotamers a) and b), characterized by two different Fa and Fb protons (Figure S44). NMR analysis confirmed the connectivity through characteristic couplings between the abstracted Hs (Fa and Fb) and the guanine C2/C6-atoms (Figure 13A-D). The key 3JCH couplings supporting the structural assignment are reported in Figure 13E

4-((2-amino-9-((2R,4S,5R)-4-hydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)-9H-purin-6-yl)oxy)-N-methyloct-7-ynamide
Identifier	#dG3
¹H NMR (700 MHz, CD₃OD)	δ (ppm): 8.04 (s, 1H), 6.31 (dd, J = 8.1, 6.0 Hz, 1H), 5.59 (tt, J = 8.0, 4.5 Hz, 1H), 4.56 (dt, J = 5.3, 2.5 Hz, 1H), 4.04 (q, J = 3.0 Hz, 1H), 3.84 (dd, J = 12.3, 3.0 Hz, 1H), 3.74 (dd, J = 12.3, 3.4 Hz, 1H), 2.80 (ddd, J = 13.6, 8.0, 5.8 Hz, 1H), 2.67 (s, 3H), 2.38 – 1.96 (m, 10H)
¹³C NMR (176 MHz, CD₃OD)	δ (ppm): 175.91, 162.39, 161.41, 154.38, 140.07, 115.99, 89.72, 86.92, 84.18, 75.42, 73.19, 69.88, 63.78, 41.13, 34.30, 32.44, 30.92, 26.33, 15.41
HRMS (ESI, m/z)	calcd. for formula C₁₉H₂₆N₆O₅ [M-H]⁺ = 419.2037; found = 419.2045

4-((2-amino-9-((2R,4S,5R)-4-hydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)-9H-purin-6-yl)oxy)-N-methyloct-7-ynamide
Identifier	#dG4
¹H NMR (700 MHz, CD₃OD)	δ (ppm): 8.05 (s, 1H), 6.32 (dd, J = 8.1, 6.0 Hz, 1H), 5.58 (tt, J = 8.0, 4.5 Hz, 1H), 4.56 (dt, J = 5.4, 2.5 Hz, 1H), 4.04 (q, J = 3.0 Hz, 1H), 3.84 (dd, J = 12.2, 3.1 Hz, 1H), 3.74 (dd, J = 12.2, 3.4 Hz, 1H), 2.79 (ddd, J = 13.7, 8.1, 5.8 Hz, 1H), 2.67 (s, 3H), 2.38 – 1.97 (m, 10H)
¹³C NMR (176 MHz, CD₃OD)	δ (ppm): 175.91, 162.36, 161.43, 154.38, 140.04, 115.93, 89.71, 86.85, 84.18, 75.43, 73.17, 69.88, 63.76, 41.18, 34.28, 32.44, 30.91, 26.33, 15.41
HRMS (ESI, m/z)	calcd. for formula C₁₉H₂₆N₆O₅ [M-H]⁺ = 419.2037; found = 419.2044

4-((2-amino-9-((2R,4S,5R)-4-hydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl)-9H-purin-6-yl)oxy)-N-methyloct-7-ynamide
Identifiers	#dG3 and #dG4
NMR	The secondary adducts, #dG3 and #dG4 (Figure S45), were identified as C6O-alkylation products based on the warhead carbon chemical shift (~75.4 ppm) and its correlation to the C6-carbonyl (Figure 14)

Seq 22AG
Calculated mass	6966.4 Da
Measured mass	6967.3 Da

Seq 22AG-Alkylated
Measured mass	7620.2 Da
PDC-4-N2 adduct	652.9 Da

Seq cMyc
Calculated mass	6991.4 Da
Measured mass	6991.4 Da

Seq cMyc-Alkylated
Measured mass	7644.6 Da
PDC-4-N2 adduct	653,2 Da

Seq 25CEBwt
Calculated mass	8258.2 Da
Measured mass	8258.2 Da

Seq 25CEBwt-Alkylated
Measured mass	8911.4 Da
PDC-4-N2 adduct	653,2 Da

Bp-COOH
Transient spectrum	Full transient spectrum of the nπ* triplet excited state of Bp-COOH (3.5 mM). It presents a first species, which is the nπ* triplet excited state, exhibiting a maximum at 545 nm and at λ > 740 nm. The second long living species is the ketyl radical, exhibiting maximum absorption at 570 nm and at 720 nm

Bp-CONHMe
Transient spectrum	Full transient spectrum of the nπ* triplet excited state of the Bp-CONHMe (3.5 mM) without oxygen recorded in function of the time. It presents a first species with a maximum at 545 nm and over 740 nm, which decays after tens of microsecond, and a second species is present with a maximum at 570 nm and at 720 nm

cMyc
Chromatogram (detection 260 nm)	cMyc retention time 16.55 min

Alkylated cMyc
Chromatogram	The alkylated adduct with the retention time above 40 min is indicated in purple
UV spectrum	UV spectrum of the alkylated photoadduct where is possible to distinguish the characteristic absorption of dG (from 250 nm to 300 nm) and an absorption tail with a maximum at 350 nm representing the absorption of the in-line compound PDC-4-N2

Alkylated cMyc
RP-HPLC	The digested photoproducts displayed much longer elution times in RP-HPLC as compared to the unmodified deoxynucleosides, and only one peak was clearly detected and isolated from the reaction mixture (Figure S62A-B; retention time 47 min)
UV spectrum	The UV spectrum of the photoadduct clearly showed that the alkylation of PDC-4-N2 occurs on dG (Figure S62C)