Abstract Recently, we presented a novel enantioselective multicomponent reaction of phthalazines, aldehydes and thiols accessing thioether‐substituted 1,2‐dihydronaphthalenes. Herein, comprehensive investigation on the mechanism this domino inverse electron‐demand (IEDDA)/thiol transfer is disclosed. In particular, origin stereochemical outcome has been rationalized, as well structural requirem...

An efficient synthesis of the tetracyclic steroid core, 19, of rhodexin A and sarmentogenin is reported. An initial inverse-electron-demand Diels-Alder reaction of the acyldiene 6 with the silyl enol ether 7a gave the cycloadduct 8 with the required four contiguous stereocenters in a single step. This compound was then transformed into the methylated enedione 13 which afforded after a reductive...

The first successful inverse electron-demand Diels-Alder has been demonstrated with the 2-pyrone methyl coumalate in conjunction with substituted indoles. Utilizing 1-alkyl-3-chloroindoles as the electron-rich dienophile efficiently generates carbazoles without the need for additional metal catalysts. Through a thermal, one-pot Diels-Alder/decarboxylation/elimination domino sequence, access to ...