4.3.1. BF2-Bodipy **11**

This compound was prepared according to our previously described method [38], from phthalide and pyrrole.

#### 4.3.2. Mannopyranosyl BODIPY **12**

This compound was prepared by glycosylation of BODIPY **11** (26 mg, 0.088 mmol) with orthoester **4c** (100 mg, 0.178 mmol), according to the general procedure for glycosylation, procedure A. Flash chromatography (hexane- ethyl acetate; 85:15) yielded BODIPY-mannoside **12** (64 mg, 80%). <sup>1</sup>H-NMR (500 MHz, CDCl3) δ 8.05–7.16 (m, 24H), 6.68 (dd, *J* = 12.4, 4.2 Hz, 2H), 6.47 (dd, *J* = 4.2, 1.8 Hz, 1H), 6.33 (dd, *J* = 4.3, 1.8 Hz, 1H), 5.40 (dd, *J* = 3.1, 1.9 Hz, 1H), 4.86 (d, *J* = 1.9 Hz, 1H), 4.79 (d, *J* = 10.7 Hz, 1H), 4.72–4.65 (m, 3H), 4.52–4.42 (m, 4H), 4.37 (d, *J* = 11.8 Hz, 1H), 4.01 (t, *J* = 9.6 Hz, 1H), 3.88–3.75 (m, 3H), 3.58 (dd, *J* = 10.9, 1.9 Hz, 1H), 3.50–3.44 (m, 1H) <sup>13</sup>C-NMR (125 MHz, CDCl3) δ 165.7, 145.3, 145.2, 144.8, 138.7, 138.6, 138.2, 135.7, 135.4, 133.2, 132.9, 132.6, 131.2, 131.0 (×2), 130.2, 130.1 (×2), 130.0, 128.9, 128.5, 128.4 (×5), 128.2 (×2), 127.9, 127.7 (×2), 127.6 (×2), 119.2, 118.8, 97.5, 78.1, 75.3, 74.1, 73.5, 72.0, 71.6, 68.8 (×3), 68.3, 67.3, 51.1, 29.8; <sup>19</sup>F-NMR (376 MHz, CDCl3) δ −145.4 (q, *J*B–F = 28.9 Hz), −145.4 (q, *J*B–F = 28.9 Hz); HRMS (ESI-TOF): calc for C50H49BF2N3O<sup>7</sup> [M + NH4] + ; 852.37407 found 852.36969.

#### 4.3.3. Mannopyranosyl BODIPY **13**

This compound was obtained when applying the general procedure for debenzoylation, procedure B, to BODIPY-mannoside **12** (60 mg, 0.087 mmol) followed by flash chromatography (hexane- ethyl acetate; 6:4). Compound **13** (56 mg, 78%): <sup>1</sup>H-NMR (300 MHz, CDCl3) δ 8.04–7.12 (m, 24H), 6.66 (ddd, *J* = 10.4, 4.2, 1.1 Hz, 2H), 6.48 (ddd, *J* = 4.2, 1.8, 0.7 Hz, 1H), 6.43 (ddd, *J* = 4.2, 1.8, 0.7 Hz, 1H), 5.42 (dd, *J* = 3.1, 2.0 Hz, 1H), 4.87–4.77 (m, 2H), 4.74–4.60 (m, 3H), 4.51–4.36 (m, 4H), 4.04 (t, *J* = 9.5 Hz, 1H), 3.98–3.88 (m, 1H), 3.78 (dd, *J* = 10.6, 3.5 Hz, 1H), 3.66–3.53 (m, 2H) 3.12 (s, 3H), 3.03 (s, 3H); <sup>19</sup>F-NMR (376 MHz, CDCl3): showed not peaks at all; HRMS (ESI-TOF): calc for C52H51BN2NaO<sup>9</sup> [M + Na]<sup>+</sup> ; 881.35682 found 881.35690.

#### 4.3.4. Mannopyranosyl BODIPY **14**

Treatment of compound **12** (80 mg, 0.096 mmoles) with sodium methoxide in MeOH, at 65 ◦C for 1 h resulted in the consumption of the starting material. Then, addition of solid NH4Cl and stirring for 15 min followed by filtration and solvent evaporation provided a residue that was purified by chromatography on silica gel (hexane-ethyl acetate; 3:7) to give dimethoxyboron-derivative **14** (56 mg, 78%). <sup>1</sup>H-NMR (300 MHz, CDCl3) δ 7.88–7.03 (19H), 6.68 (dd, *J* = 4.2, 1.3 Hz, 1H), 6.60 (dd, *J* = 4.2, 1.3 Hz, 1H), 6.42 (dt, *J* = 4.3, 1.8 Hz, 1H), 4.74 (d, *J* = 10.8 Hz, 1H), 4.59–4.35 (m, 9H), 3.78–3.50 (m, 6H), 3.38–3.33 (m, 1H), 3.20 (s, 3H), 3.06 (s, 3H); <sup>13</sup>C-NMR (125 MHz, CDCl3) δ 152.8, 144.9, 144.5, 136.7, 136.6, 135.7, 133.7, 133.6, 130.4, 130.0, 129.8, 129.7, 129.4, 128.5 (×2), 128.4 (×2), 128.3 (×2), 128.1 (×2), 128.0 (×2), 127.8 (×2), 127.7 (×2), 118.5, 118.1, 100.6, 79.9, 75.2, 74.1, 73.6, 71.7, 71.4, 69.1, 68.5, 68.3, 67.3, 50.3, 49.8 HRMS (ESI-TOF): calc for C45H47BN2NaO<sup>8</sup> [M + Na]<sup>+</sup> ; 777.33254 found 777.33546.
