Skip to main content
. Author manuscript; available in PMC: 2020 Apr 30.
Published in final edited form as: J Am Chem Soc. 2019 Jun 3;141(23):9191–9196. doi: 10.1021/jacs.9b04508

Scheme 2. (A) Total Synthesis of (+)-Granatumine A (6); (B) Structural Revision of (+)-Xylogranatin F (29) and (+)-Xylogranantin G (28)a.

Scheme 2.

aReagents and conditions: (7) ethylenediammonium diacetate (0.7 equiv), 9 (1.5 equiv), (CH2 Cl)2, 65 °C, 4 h, 47%; (8) LiBH4 (4.5 equiv), CeCl3·7H2O (4.5 equiv), CF3CH2OH/THF (1:1), 0 to 23 °C, 3 h, 61%; (9) HO-NH2·HCl (5.0 equiv), LiOAc·H2O (6.0 equiv), MeOH, 80 °C, 12 h, 34% 4 + 35% 26; (10a) SOCl2 (7.0 equiv), CH2Cl2, 40 °C, 12 h, then NaOMe (10.0 equiv), MeOH, 70 °C, 5 h, 82%, 1:1 dr; (10b) Zn (4.0 equiv), CeCl3·7H2O (2.0 equiv), MeOH, 23 °C, 6 h, 67%; (10c) SOCl2 (7.0 equiv), CH2Cl2, 40 °C, 12 h, then Zn(OAc)2 (10.0 equiv), AcOH, 100 °C, 12 h, 74%, 1:1 dr; (11) K2CO3 (7.0 equiv), MeOH, 60 °C, 5 h, 87%.