SCHEME 3.

Synthesis of 3- and 4-deoxyglucal derivatives.^a

^a Reagents and conditions: (a) NaH, CS, MeI, THF, rt; (b) Bu SnH, AIBN, PhCH, reflux (54% isolated yield for 8, 82% for 11); (c) BH₃-THF, Bu₂BOTf, THF, −78 ºC; (d) BnBr, Bu₄NI, NaH, THF, rt (73% over 2 steps); (e) BnBr, Bu₄NI, NaH, DMF, rt; (f) iBu₂AlH, CH₂Cl₂, 0 ºC; (g) same as step (e); (h) DDQ, tBuOH, pH 7 phosphate buffer, CH₂Cl₂, rt (61% over 4 steps). PMB = p-methoxybenzyl; PMP = p-methoxyphenyl.