A study was conducted to gain insight into the preparative potential of photosensitized reactions of acyclic N-benzylglycinates containing an a-trimethylsilyl group with dimethyl acetylenedicarboxylate (DMAD). The photosensitizers employed in the reactions include 9,10-dicyanoanthracene (DCA), 1,4dicyanonaphthalene (DCN), rose bengal (RB) and fullerene C 60 . The results show that photoirradiation of oxygenated solutions containing the photosensitizers, glycinates and dimethyl acetylenedicarboxylate leads to competitive formation of pyrroles and b-enamino-esters. The distributions of pyrrole and benamino-ester products formed in these reactions are highly influenced by the electronic nature of the phenyl ring substituent on the benzylglycinates and the photosensitizer used. These photoaddition reactions take place via mechanistic pathways involving competitive formation of azomethine ylides and secondary amines, generated by a mechanistic routes involving initial SET from the benzylglycinates to photosensitizers.Scheme 1 Photoinduced single electron transfer (SET) reaction pathways opened for amine substrates. Scheme 2 SET-promoted 1,3-dipolar cycloaddition reactions of ethyl 2-(3,4-dihydroisoquinolin-2(1H)-yl)acetate 6 with dipolarophile. Scheme 3 SET-promoted 1,3-dipolar cycloaddition reactions of tertiary N-benzylglycinates 10 (E ¼ H, SiMe 3 ) with fullerene C 60 . 5640 | RSC Adv., 2019, 9, 5639-5648 This journal is a 220 mL of MeCN solution containing glycinate (3.2 mM), acetylene (3.2 mM) and RB (0.32 mM). b Isolated yields. 5642 | RSC Adv., 2019, 9, 5639-5648 This journal is a 220 mL of MeCN or toluene solutions containing N-benzylamines (3.2 mM), acetylene (3.2 mM) and photosensitizer (DCA (0.27 mM), DCN (0.32 mM), RB (0.32 mM) and C 60 (0.16 mM)). b Isolated yields. This journal isScheme 7 Non-regioselective formation of iminium ions 39-41 from non-silyl amine analog 21.This journal is