Direct aromatic carbon-oxygen and carbon-hydrogen bond functionalization via organic photoredox catalyst

A method of making a compound having a structure represented by a formula:

• wherein Z is selected from halogen, —CN, —NH2, C1-C4 alkylamino, and (C1-C4)(C1-C4) dialkylamino, provided that when Z is —NH2, C1-C4 alkylamino, or (C1-C4)(C1-C4) dialkylamino, then Z contains a radioisotope;
• wherein each of R30a, R30b, R30c, R30d, and R30e is independently selected from hydrogen, halogen, —CN, —NO2, C1-C8 alkyl, C1-C8 alkoxy, —O—(C1-C8 alkyl)-CO2—(C1-C8 alkyl), —C(═O)R10, —C(═O)OR11, —C(═O)NR12aR12b, Ar2, and —CH2CR13(NR14aR14b)CO2R15;
• wherein each of R10, R11, R12a, R12b, R13, and R15, when present, is independently selected from hydrogen and C1-C4 alkyl;
• wherein each of R14a and R14b, when present, is independently selected from hydrogen, C1-C4 alkyl, and amine protecting group;
• and
• wherein Ar2, when present, is selected from aryl and heteroaryl, and substituted with 0, 1, 2, or 3 groups independently selected from halogen, —CN, —NO2, —OH, —SH, —NH2, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 cyanoalkyl, C1-C4 alkoxy, C1-C4 hydroxy, C1-C4 thioalkoxy, C1-C4 alkylthiol, C1-C4 aminoalkyl, C1-C4 alkylamino, and (C1-C4)(C1-C4) dialkylamino;
• the method comprising the step of reacting an arene having a structure represented by a formula:
• wherein each of R30a, R30b, R30c, R30d, and R30e is independently selected from hydrogen, halogen, —CN, —NO2, C1-C8 alkyl, C1-C8 alkoxy, —O—(C1-C8 alkyl)-CO2—(C1-C8 alkyl), —C(═O)R10, —C(═O)OR11—C(═O)NR12aR12b, Ar2, and —CH2CR13(NR14aR14b)CO2R15;
• wherein E is an electron donating group is selected from —OR20, —SO3R20, —SR20, —NR21aR21b, —OC(═O)R20, —OC(═O)OR20, —OC(═O)SR20, and —OC(═O)NHR20;
• wherein R20, R21a, and R21b, when present, is independently selected from hydrogen, C1-C8 alkyl, C1-C8 alkenyl, and Ar3;
• and
• wherein Ar3, when present, is selected from aryl and heteroaryl, and substituted with 0, 1, 2, or 3 groups independently selected from halogen, —CN, —NO2, —OH, —SH, —NH2, —CHO, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 cyanoalkyl, C1-C4 alkoxy, C1-C4 hydroxy, C1-C4 thioalkoxy, C1-C4 alkylthiol, C1-C4 aminoalkyl, C1-C4 alkylamino, and (C1-C4)(C1-C4) dialkylamino,
• with a nucleophile selected from a halide, a cyanide, and an amine,
• in the presence of a visible light source and a catalytically effective amount of an acridinium photocatalyst, and under anaerobic conditions, thereby forming the compound.