The transition metal-catalysed skeletal reorganization of 1,6-enynes can lead to three types of products - a type I product occurring via the cleavage of the alkene C-C bonds and the migration of the terminal alkene carbon to the terminus of the alkyne; a type II product arising from cleavage of both the double and the triple bonds followed by insertion of the terminal alkene carbon into the alkyne C-C triple bond; and a type III product which is obtained when there is a cleavage of the olefinic bond followed by formation of two new bonds from each carbon to each of the acetylenic carbons. The course of these reactions is highly dependent on the metal catalyst used and type of substitution at the alkene and alkyne moieties of the enyne. In this mechanistic study of the re-organization of 1,6-enynes catalysed by GaCl, performed at the DFT M06/6-311G(d,p) level of theory, the parent reaction selectively leads to the formation of the type I product through the formation of the open cyclopropane ring.
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