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After the initial formation of an ether\u2013BBr<jats:sub>3<\/jats:sub> adduct, secondary and tertiary alkyl ethers are cleaved through Br<jats:sup>\u2013<\/jats:sup> transfer from the activated BBr<jats:sub>3<\/jats:sub> to the alkyl moiety, as postulated in the literature. In contrast, all other ethers studied react through a novel pathway involving two ether\u2013BBr<jats:sub>3<\/jats:sub> adducts, one of which acts as Br<jats:sup>\u2013<\/jats:sup> donor, and the second as the reaction substrate. The identification of the novel bimolecular mechanism for this classical reaction has further applications, because it implies that BBr<jats:sub>3<\/jats:sub>\u2010assisted ether cleavage may become impossible if the ether is surrounded by bulky portions of the molecule that prevent the approach of the attacking BBr<jats:sub>3<\/jats:sub> adduct. Our data also allow the construction of an order of reactivity of alkyl ether deprotection: isopropyl, benzyl, tertiary alkyl, allyl, isobutyl and ethyl can be removed sequentially as their bromo derivatives; phenyl, cyanomethyl and chloromethyl groups can be sequentially removed as their corresponding alcohols.<\/jats:p>","DOI":"10.1002\/ejoc.201300337","type":"journal-article","created":{"date-parts":[[2013,5,31]],"date-time":"2013-05-31T09:41:35Z","timestamp":1369993295000},"page":"5195-5199","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":14,"title":["BBr<sub>3<\/sub>\u2010Assisted Cleavage of Most Ethers Does Not Follow the Commonly Assumed Mechanism"],"prefix":"10.1002","volume":"2013","author":[{"given":"Carla","family":"Sousa","sequence":"first","affiliation":[]},{"given":"Pedro J.","family":"Silva","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2013,5,31]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01257a035"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4020(68)88130-X"},{"key":"e_1_2_6_3_2","first-page":"609","author":"Youssefyeh R. 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