Alkyne anions reaction with aryl halides

Terminal alkynes 170 undergo the substitution with aryl and alkenyl halides to form arylalkynes and enynes in the presence of Cul, as described in Section 3.3.1. However, the insertion of terminal alkynes 170 occurs in the absence of Cul, and the alkenylpalladium complex 171 is formed as an intermediate, which cannot be terminated by itself and must undergo further reactions, such as alkene insertion or anion capture. These reactions of terminal and internal alkynes with intermediates 172 and 173 are summarized in Schemes 3.7 and 3.8. 

Mixed-ligand anions [RC=CAuX] are rare in organogold chemistry. Selected examples have been obtained from reactions of [RC=CAuL oligomers with halides Q+X, from Q[Au(acac)2] salts with alkynes, followed by acids HX in the molar ratio 1 1 1, and from complexes (tht)AuCl (tht = tetrahydrothiophene) or [(Ph3P)2C]AuCl with an alkyne and a base (1 1 1). Known examples of products include salts Q+[HC=CAuCl/Br]-72 and [(Ph3P)2CH]+[PhC=CAuCl]. 52,53 Anions with mixed alkynyl/aryl substituents are present in... 

The first alkyne cyclisations, from 377, 379 and 381, predate the early alkene cyclisations by a couple of years these three date from 1966173 and 1967,174 and illustrate the favourability of both exo and endo-dig cyclisation. All three generate benzylic vinyllithiums (378, 380 and 382), and both aryl (377, 379) and alkyl halides (381) are successful starting materials. Similar organomagnesium cyclisations were described at about the same time.175 However, it is not clear in these reactions how much of the product is due to participation of radicals in the mechanism - alkylbromides undergo halogen-metal exchange with alkyllithiums via radical intermediates (chapter 3).176 If it really is an anionic cyclisation, cyclisation to 378 is remarkable in being endo. Endo-dig anionic cyclisations are discussed below. 

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