With the established optimized conditions for decarboxylative enamide formation in hand, we proceeded to explore the scope of various natural and non-natural amino acids (Scheme 1). Both Cbz-and Boc-protected phenylalanine (2a and 2b), notably, exhibited excellent performance with exclusive (Z)-selectivity in up to 73% isolated yield. This methodology demonstrated good tolerance towards a variety of phenylalanine derivatives and both electron-donating groups (7 and 8) and electron-withdrawing groups (9-13) were applicable in up to 78% isolated yield with high (Z)-selectivity. Gratifyingly, this approach is compatible with Bpin (4,4,5,5-tetramethyl-1,3,2-dioxaboryl) substituted-phenylalanine 12, enabling future Suzuki cross-coupling reactions to construct new molecular entities. Additionally, nitrile substituted phenylalanine 13 exhibited excellent yield, however with moderate stereoselectivity, which hints to the electronic dependence of the photoisomerization. As described above, diphenylalanine 5 exhibits excellent yield. Delightfully, our method can be extended to (non-)natural amino acids with a γ-carbonyl group resulting in α,β-unsaturated products 14 and 15, although with exclusive (E)-selectivity for the acyclic one. Heteroaromatic and fused compounds showed either lower yield or lower selectivity. Pyridyl-substituted product 16 gave only 30% isolated yield, but with high stereoselectivity. Fused-aromatic systems like 2-naphthyl-alanin (Nal)-and tryptophan (Trp)-derived products 17 and 18 feature excellent yields with moderate (Z)-selectivity. Most likely, products with expanded π-character exhibit facile backisomerization from the (Z)-isomer and thus result in poor selectivity. While cyclic unfunctionalized substrates showed decreased reactivity (Scheme S6, vide infra), dihydroisoquinoline 19 exhibits lower yield compared to indane 20 and tetralin 21, indicating that ring-strain is no limitation for the β-H elimination step. Among them, tetralin 21 underwent decarboxylative elimination followed by dehydrogenation to yield naphthalene, indicating a subsequent aromatization mechanism. Control experiments demonstrate that all reaction components are crucially required for the successful decarboxylative dehydrogenation reactivity, since without light, both catalysts, or without aryl halide no product was obtained (Scheme S4). In the absence of X4, 15% yield of product 2b may be attributed to enhanced substrate solubility in DME and high basicity of BTMG. Likewise, initial decarboxylation is key, since N-Boc 2phenyl ethylamine itself does not convert to 2b under the optimized conditions (Scheme S5).