140706-86-1Relevant academic research and scientific papers
Discovery of orthogonal synthesis using artificial intelligence: Pd(OAc)2-catalyzed one-pot synthesis of benzofuran and bicyclo[3.3.1]nonane scaffolds
Takabatake, Tetsuhiko,Fujiwara, Keisuke,Okamoto, Sho,Kishimoto, Ryo,Kagawa, Natsuko,Toyota, Masahiro
, (2020)
A synthetic route for the common intermediate, methyl 2-formylbenzofuran-7-carboxylate (7a), to efficiently assemble three bioactive benzofurans 4–6 was explored using the artificial intelligence system SYNSUP. Among the routes proposed by SYNSUP, we investigated a three-step synthesis of 7a using methyl 4-ally-3-oxohept-6-enoate (10). A new catalytic reaction was found in which 7a was directly obtained from 10 in a single step with a yield of 24percent. It was found that this chemical yield could be increased to 74percent when methyl 3-allyl-2-hydroxybenzoate (9a), an intermediate of the above one-pot transformation, was subjected to the catalytic process. In addition, in this catalytic process, 8a (76percent) and 11 (77percent) were each selectively synthesized from 10 by changing only the solvent. Therefore, we created a novel orthogonal synthesis of methyl 2-methylbenzofuran-7-carboxylate (8a) and methyl 9-oxobicyclo[3.3.1]nona-3,6-diene-1-carboxylate (11). Finally, the total syntheses of bioactive benzofurans 4–6 were completed smoothly using 7a and 8a.
Mn(III)-based oxidative free-radical cyclizations of γ,γ-bis(allylic) acetoacetates
Dombroski,Snider
, p. 1417 - 1426 (2007/10/02)
Oxidative free-radical cyclizations of γ,γ-(bis)allylic acetoacetates demonstrate that 1,1-disubstituted double bonds are much more reactive than mono- or chloroalkyl-substituted double bonds. The products isolated suggests that bicyclo[3.2.1]octanes 25, 31, 33 and 36 are formed from boat cyclohexyl radical 42 and tandem cyclization products 30, 37 and 38 are obtained from boat cyclohexyl radical 41.
