“…Our investigation was initiated by the serendipitous discovery with N-alkoxylphthalimide 1 as the alkoxyl radical precursor, which can be readily prepared from alcohols and are bench-stable (Scheme 2) (Zhu et al., 2009, Kim et al., 1998, Zhang et al., 2016, Zhang et al., 2017, Wang et al., 2016, Ito et al., 2018, Han et al., 2019, Deng et al., 2019, Shi et al., 2019). Under the reaction conditions of fac -Ir(ppy) 3 and Hantzsch ester known to generate alkoxyl radicals (Zhang et al., 2016, Zhang et al., 2017, Wang et al., 2016, Ito et al., 2018, Han et al., 2019, Deng et al., 2019, Shi et al., 2019), the ester-derived N-alkoxylphthalimide 1 gave no δ-C(sp 3 )-H allylation adduct 3 with allyl sulfone 2 under blue LED irradiation. Instead, the α-C(sp 3 )-H allylation adduct 4 was observed in 41% yield, together with the hydrogenation adduct alcohol 5 in 52% yield (entry 1 in Table 1) (Zhang et al., 2016).…”