AbstractThe syntheses and olfactory evaluations of eight new macrocyclic musks with a 1,6‐dioxa structure (1a–d and 1′a–d) as well as of twelve optically active 3‐methyl macrolides (5a–c and 5′a–c) are reported. These macrocycles were synthesized via intramolecular metathesis mediated by the Grubbs catalyst. Despite the absence of a CO function, the 1,6‐dioxa compounds, both unsaturated (1) and saturated (1′), possess musky odors similar to those of macrocyclic ketones and lactones. Especially 16‐membered rings were found to display an intense and pleasant musk character. However, in the case of optically active 3‐methyl macrolides (5, 5′), only the (R)‐configured 15‐ and 16‐membered rings had intense and pleasant musk notes.