RESUMO
An efficient protocol for the chemoselective construction of the indeno[1,2-b]pyrroles and rearranged indeno[1,2-b]pyrrole derivatives is reported via an N-acylation/cyclization/Wittig reaction. Extensive mechanistic investigations revealed that the initially formed crucial spiro-indene-1,2'-[1,3,4]oxadiazol intermediate further reacts with phosphine to generate betaine, thus predominately resulting in the aforementioned heteroarenes proceeding by a Wittig reaction.
RESUMO
A new method for the construction of functionalized furo[3,2-c]coumarins via MBH-type/acyl-transfer/Wittig reaction is reported. The current approach would open a new route for the simultaneous formation of two rings in a one-pot reaction which is accompanied by incorporation of a keto functionality on the furan ring by activating the terminal alkynoates with phosphine. Furthermore, this protocol could also be applicable to the internal alkynoates/propiolamides to generate the 2,3-disubstituted furo[3,2-c]coumarins/furo[3,2-c]quinolinones by excluding the acyl-transfer reaction.
RESUMO
A new type of all-carbon 1,3-dipole precursor, 3-homoacylcoumarin, was employed for the stereoselective (3+2) cycloaddition with indandione alkylidenes to generate a series of coumarin/indandione-fused spirocyclopentanes bearing four contiguous stereogenic centers. While two reaction pathways progressed simultaneously, detailed mechanistic investigation revealed that the highly efficient stereoselective concerted route dominated the extremely slow stepwise pathway.