Bismuth mediated barbier synthesis of α-homoallylic alcohols via a sigmatropic rearrangement in [bmim][HSO₄]

Zinc/Bismuth-Mediated Allylation Reaction of Biomass Feedstocks: Synthesis of Furanic Diols

“…Similar Bi-mediated Barbier-type reaction undergoes a-substitution as opposed to −substitution (reported here for 32 and 33). 18,19 To our knowledge, such mono-allylation of dialdehydes are not known. This interesting result motivated us to apply the protocol to aryl dicarboxaldehydes to synthesize corresponding mono-allylated derivatives.…”

“…Hence, we envisioned that another metal with milder reactivity, such as bismuth, could be used for selective monoallylation. To our delight, when allyl bromide and DFF (18) were combined in 1:1 molar ratio in the presence of Bi and NH 4 I in DMF-H 2 O solvent mixture, the monoallylated product 31 was obtained exclusively in 81% yield (Scheme 5). Similar reaction…”

“…Similar Bi-mediated Barbier-type reactions undergo -substitution as opposed to -substitution (reported here for 32 and 33). 18,19 To our knowledge, such monoallylations of dialdehydes are not known.…”

“…In a similar manner, the optimized reaction protocol was applied to the dialdehyde DFF (18) to synthesize the respective furyl diols (Scheme 3). It was noticed that all the furyl diols 19-24 were obtained in excellent yields (75-85%).…”

“…Scheme 5 Bi-mediated monoallylation reaction with DFF (18) This interesting result motivated us to apply the protocol to aryl dicarboxaldehydes to synthesize the corresponding monoallylated derivatives. Hence, terephthaldehyde and isophthaldehyde were treated separately under the developed conditions with bismuth and 1 equivalent of allyl bromide.…”