*3.6. Preparations of the (S)- and (R)-PGME Amides of Compounds* **7** *and* **8**

To a dry DMF solution (500 μL) of compound **7** (0.6 mg, 1.6 μM) and (*S*)-PGME (1.4 mg, 7.4 μM), PyBOP (3.8mg, 7.4 μM), HOBT (1.0mg, 7.4 μM), and *N*-methylmorpholine (100 μL) were added. After stirring the mixture for 3 h at room temp, a 5% HCl solution and EtOAc were added to the reaction mixture. The EtOAc layer was subsequently washed with saturated NaHCO3 solution and brine. The organic layer was dried over anhydrous Na2SO4. After removing the solvent under vacuum, the residue was purified by reversed-phase HPLC (YMC-ODS column, 4.6 × 250 mm; H2O-MeOH, 35:65) to give (*S*)-PGME amide **7**-18*S* (0.3 mg). Compound **7**-18*R* (0.4 mg), the (*R*)-PGME amide of **7**, was prepared from (*R*)-PGME in a similar fashion. Compounds **8**-18*S* and **8**-18*R* (0.3 mg each), the (*S*) and (*R*)-PGME amides of 5, respectively, were also prepared using this method.

#### 3.6.1. (*S*)-PGME Amide of **7** (**7**-18*S*)

Brown amorphous solid; 1H NMR (CD3OD, 800 MHz) δ<sup>H</sup> 7.371–7.329 (5H, m, PGME-Ar), 5.427 (1H, s, PGME-H-1), 5.202 (1H, dq, *J* = 8.6, 1.1 Hz, H-12), 4.802 (1H, td, *J* = 9.0, 4.1 Hz, H-11), 4.299 (1H, t, *J* = 5.1 Hz, H-4), 3.945 (1H, dd, *J* = 4.6, 1.6 Hz, H-8), 3.681 (3H, s, PGME-OMe), 2.612 (1H, m, H-2α), 2.592 (1H, d, *J* = 17.8 Hz H-7α), 2.456 (1H, m, H-17), 2.419 (1H, dd, *J* = 13.7, 9.4 Hz, H-10α), 2.309 (1H, ddd, *J* = 16.9, 6.9, 4.8 Hz, H-2β), 2.230 (1H, dd, *J* = 18.0, 4.6 Hz, H-7β), 2.169 (1H, m, H-3α), 2.090 (1H, dd, *J* = 13.7, 4.1 Hz, H-10β), 2.005 (2H, m, H-14), 1.964 (1H, m, H-3β), 1.669 (3H, d, *J* = 1.2 Hz, H-20), 1.589 (1H, m, H-16α), 1.454 (2H, m, H-15), 1.354 (3H, s, H-19), 1.332 (1H, m, H-16β), 1.049 (3H, d, *J* = 6.9 Hz, H-21); LRESIMS *m*/*z* 526.3 [M + H]+.
