Insertion of alkynes into a Cu–Al bond and functionalisation to a copper acyl Caitilín McManus, Agamemnon E. Crumpton, Simon Aldridge University of Oxford, UK Alkenyl aluminium reagents are used in synthesis for the further functionalization of alkenes, finding use in alkylation and transmetallation reactions. 1 Likewise, copper alkenyl species have been proposed as intermediates in carbometallation reactions. 2 We recently reported a directly bonded Al – Cu bonded complex, formed from a potassium aluminyl anion and ( t Bu 3 P)CuI. 3 In this work, this copper aluminyl compound was shown to react with internal alkynes, producing unsymmetrically dimetallated alkenes. This represents the first example of insertion of an alkyne into an Al–M bond, and also of an olefin bearing both aluminium and copper substituents. The presence of two different metals allows for differential reactivity at each carbon of the C=C bond, leading to selective reaction with CO to form copper acyl compounds.
References 1. Zweifel, G.; Miller, J.A.; in Organic Reactions ed. Dauben W.G. Wiley, 1984 , Vol 32, Chapt. 2, 376-430 2. Seuss, A. M.; Uehling, M. R.; Kaminsky, W.; Lalic, G.; J. Am. Chem. Soc. 2015 , 137 , 7747−7753 3. McManus, C.; Hicks. J; Cui,X.; Zhao, L.; Frenking, G.; Goicoechea, J. M., Aldridge, S.; Chem. Sci. , 2021 , 12, 13458–13468
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