The reaction of the title compound (1) with an excess of lithium powder and a catalytic amount of naphthalene (2.5%) in the presence of an electrophile [E 1 + =Bu t CHO, Et 2 CO, (CH 2 ) 5 CO, PhCOMe, Me 3 SiCl] in THF at -78 to -30°C, followed by treatment with a second electrophile [E 2 + =Bu t CHO, Me 2 CO, Et 2 CO, (CH 2 ) 4 CO, (CH 2 ) 5 CO, Bu t COMe, Bu t 2 CO, PhCH=NPh, Me 3 SiCl, D 2 O] at -30°C to room temperature leads, after hydrolysis, to the expected compounds 2. For carbonyl derivatives, compounds 2 were successively hydroborated (BH 3 THF) and oxidised [33% H 2 O 2 and then PCC or RuCl 2 (PPh 3 ) 3 ] to give directly the corresponding perhydrofurofurans 4.