2-chloromethyl-3-(2-methoxyethoxy)propene: Naphthalene-catalysed lithiation and reaction towards electrophiles

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(+)=(BuCHO)-C-t, Et2CO, (CH2)(5)CO, PhCOMe, Me3SiCl] in THF at -78 to -30 degrees C, followed by treatment with a second electrophile [E-2(+)=(BuCHO)-C-t, Me2CO, Et2CO, (CH2)(4)CO, (CH2)(5)CO, (BuCOMe)-C-t, (Bu2CO)-C-t, PhCH=NPh, Me3SiCl, D2O] at -30 degrees C to room temperature leads, after hydrolysis, to the expected compounds 2. For carbonyl derivatives, compounds 2 were successively hydroborated (BH3 . THF) and oxidised [33% H2O2 and then PCC or RuCl2(PPh3)(3)] to give directly the corresponding perhydrofurofurans 4. (C) 1998 Elsevier Science Ltd. All rights reserved.