Arene Activation through Iminium Ions: Product Diversity from Intramolecular Photocycloaddition Reactions

摘要

While 2-alk-ω-enyloxy-sustituted benzaldehydes do not display any photochemical reactivity at the arene core, the respective iminium perchlorates were found to undergo efficient reactions either upon direct irradiation (λ=366 nm) or under sensitizing conditions (λ=420 nm, 2.5 mol thioxanthen-9-one). Three pathways were found: (a) Most commonly, the reaction led to benzoxacyclic products in which the olefin in the tether underwent a formal, yet unprecedented carboformylation (13 examples, 44-99 yield). The cascade process occurred with high diastereoselectivity and was found to be stereoconvergent. (b) If a substituent resides in the 3-position of the benzene ring, a meta photocycloaddition was observed which produced tetracyclic skeletons with five stereogenic centers in excellent regio-and diastereoselectivity (2 examples, 58-79 yield). (c) If the tether was internally substituted at the alkene, an arene photocycloaddition was avoided and an azetidine was formed in an aza Paterno-Buchi reaction (2 examples, 95-98 yield).