Photolysis of the phenolic tetrahydrobenzylisoquinoline 11 in basic solution yielded (±)-de-N-methylthalphenine (14). Quaternization with methyl iodide then afforded thalphenine iodide (rac. 1) which upon Hofmann elimination supplied thaliglucine (2). Thaliglucinone (3) is obtained by oxidation of thaliglucine (2).