AbstractThe 2,3‐dihydro‐1H‐benz[f]indole‐4,9‐diones 3a–d, h were formed in a one‐step reaction in 13–82% yield by an unprecedented [3 + 2] regioselective photoaddition of 2‐amino‐1,4‐naphthoquinone (1) with various electronrich alkenes 2 (Scheme 1, Table). The [3 + 2] photoadducts derived from 1 with vinyl ethers and vinyl acetate gave 1H‐benz[f]indole‐4,9‐diones 4e, f, i, in 33–72% yield, by spontaneous loss of the corresponding alcohol or AcOH from the resulting adducts; 4i has a kinamycin skeleton. The [3 + 2] photoaddition also took place on irradiation of the differently substituted amino‐1,4‐benzoquinones 6, 7, and 12 and excess alkenes 2 in benzene, giving 1H‐indole‐4,7‐dione derivatives 13 and 14 (Scheme 3), 15a and 16 (Scheme 4), and 18 (Scheme 4), respectively. The initial products in these photoadditions were proved to be hydroquinones, the air oxidation of which yielded the heterocyclic quinones; 2,3‐dihydro‐2‐methoxy‐2‐methyl‐5‐phenyl‐1H‐indole‐1,4,7‐triyl triacetate (19) was isolated after treatment of the crude photoaddition mixture obtained from 2‐amino‐5‐phenyl‐1,4‐benzoquinone (7) and 2‐methoxyprop‐1‐ene (2f) with Ac2O and pyridine under N2. A pathway leading to the annelated hydroquinones involving ionic intermediates arising from an electron transfer in these photoadditions is proposed (Scheme 5).