Direct Trifluoromethoxylation without OCF 3 ‐Carrier through In Situ Generation of Fluorophosgene

Owing to the high interest in the OCF 3 group for pharmaceutical and agrochemical applications, trifluoromethoxylation received great attention in the last years with several new methods for this approach towards OCF 3 ‐comprising compounds. Yet, it most often requires the beforehand preparation of specific F 3 CO − transfer reagents, which can be toxic, expensive, unstable, and/or generate undesired side‐products upon consumption. To circumvent this, the in‐situ generation of gaseous fluorophosgene from triphosgene, its conversion by fluoride into the OCF 3 anion, and the direct use of the latter in nucleophilic substitutions is an appealing strategy, which, although recently approached, has not been fully exploited. We disclose herein our efforts towards this aim.