Metal catalyst-free N-allylation/alkylation of imidazole and benzimidazole with Morita–Baylis–Hillman (MBH) alcohols and acetates

A highly α-regioselective N-nucleophilic allylic substitution of cyclic MBH alcohols and acetates with imidazole or benzimidazole, in toluene at reflux with an azeotropic distillation, was successfully carried out with no catalysts or additives, affording the corresponding N-substituted imidazole derivatives in good yields. On the other hand, in refluxing toluene or methanol, the aza-Michael addition of imidazole onto acyclic MBH alcohols was performed using DABCO as an additive, leading to the corresponding 1,4-adducts in 70–84% yields

General and Efficient Transesterification of β-Keto Esters with Various Alcohols Using Et₃N as a Brønsted Base Additive

<div><p></p><p>Transesterification of β-keto esters with a wide variety of allyl, benzyl, propargyl, and alkyl alcohols using, for the first time, commercially available and inexpensive Et₃N as a Brønsted base additive, is efficiently performed in toluene at reflux. The corresponding esters are exclusively obtained in 57–98% yields with no trace amounts of γ,δ-ketones, usually expected from the decarboxylative Carroll rearrangement.</p> </div