A three-step, regioselective synthesis of 3,4-dimethylpenta-1,3-diene 1 has been developed. The
condensation of acetone diethylacetal with ethyl propenyl ether yielded, after hydrolysis of the
resulting triethoxy adduct 10, 2,3-dimethyl-2-butenal 7. Wittig reaction of 7 with methylenetriphenylphosphorane afforded desired diene 1 in 31% overall yield, easily scalable to the 10 g level.
Diels−Alder reaction of 1 with maleic anhydride in benzene was known to afford a 50:50 mixture
of “normal” (2) and “rearranged” (3) adducts. In THF as solvent, 2 has been reproducibly obtained
in over 90% yield as a 98:2 mixture with 3. 1H NMR spectroscopy (NOESY, ASIS) and molecular
modeling (MM2, AM1, ab initio) have been used jointly to determine the conformation of 2 and 3.
All are consistent with a folded structure of “rearranged” 3. On the other hand, only RHF/6-31G*
and B3LYP/6-31G* ab initio models were in agreement with NMR spectroscopy for an extended
conformation of adduct 2. In this case, neither MM2 nor AM1 models gave results consistent with
NMR: discrepancies as high as 30° were noted for some dihedrals between these models and ab
initio ones.
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