We then extended our approach to include alkyl-substituted arylthianthrenium salts 4, which served as competent reaction partners into our protocol, yielding the anticipated products 7-12 in good to excellent isolated yields. Notably, the synthesis of biaryl unnatural amino acids 13-15 was achieved in excellent yields. These amino acids bear functional groups amenable to subsequent synthetic manipulations, such as condensations and transition-metal catalyzed cross-couplings. Impressively, the aryl iodide bond, typically sensitive to reduction under photocatalytic conditions, proved to be compatible with our process. The method's adaptability was further underscored by its application to heteroatom-containing arylthianthrenium salts 4, leading to an array of phenylalanine derivatives (16-24). The yields were moderate to excellent, maintaining both high chemo-and regioselectivity. Additionally, our methodology demonstrated its robust functional group tolerance by facilitating access to a diverse set of heterocycle-containing amino acids. This collection of compounds included structures with dihydrobenzofuran, benzodioxole, chromanone, xanthone, pyridine, carbazole, indoline, and quinazoline-dione, showcasing the broad applicability and robustness of the synthetic strategy.