Markovnikov at Gold: Nucleophilic Addition to Alkenes at Au(III)
Peer reviewed, Journal article
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OriginalversjonOrganometallics. 2018, 37 (12), 1937-1947. 10.1021/acs.organomet.8b00218
The reactivity of Au(OAcF)2(tpy) (1, OAcF = OCOCF3; tpy = 2-(p-tolyl)pyridine) toward a wide variety of different alkenes with various substitution patterns and different oxygen-based nucleophiles has been investigated. These reactions are two-step processes where a ligand substitution is followed by a nucleophilic addition furnishing Au(III) complexes with C(sp3) ligands. In this work we have found that the reactions always occur trans to tpy-N while the OAcF ligand remains in place trans to tpy-C. The nucleophilic addition takes place exclusively at the most substituted side of the double bond, in a Markovnikov manner, and the nucleophilic addition occurs in an anti fashion as can be seen from the reaction with the 2,3-disubstituted alkene trans-2-hexene. This study has provided valuable insight into the scope and regiochemistry of Au(III) mediated nucleophilic additions, which is of great importance for further development of Au(III) catalysis and alkene functionalization.