Synthesis of cyclophellitol cyclosulfates 5 and 6, and inactivation of GAA by compound 5. (a)
Compounds 5 and 6 were prepared from cyclohexene 11. Reagents and conditions: (i) BnBr, TBAI, NaH, DMF, rt,
18 h, 70%; (ii) RuCl3, NaIO4, EtOAc, ACN, 0
°C, 2 h (13, 39%; 14, 26%); (iii) (a)
SOCl2, Et3N, DCM, 0 °C, (b) RuCl3, NaIO4, CCl4, ACN, 0 °C, 3 h (15, 59%; 16, 62%); (iv) H2, Pd/C, MeOH, rt,
18 h (5, 71%; 6, 72%). (b) Semilogarithmic
plots of residual activity of GAA versus time at 9, 8, 7, 6, 5, 4,
3, and 2 μM α-cyclosulfate 5. (c) Plot of
pseudo first order rate constants from panel c vs concentration of 5.