Direct β‐Selective Cross‐Coupling of Alkenyl Gold Complexes with Alkyl Electrophiles. Issue 35 (15th November 2016)

• Record Type: Journal Article
• Authors: Nguyen, Julia; Duncan, Nicole; Lalic, Gojko
• Is Part Of: European journal of organic chemistry. Issue 35(2016)
• Page Start: 5803
• Page End: 5806
• Publication Date: 2016-11-15
• Subjects: Homogeneous catalysis -- Gold -- Alkenes -- Alkylation -- Cross‐coupling; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201601149
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract : Alkenyl gold complexes are common intermediates in gold‐catalyzed transformations of allenes and alkynes, and numerous methods for their functionalization have been explored. Particularly valuable are cross‐coupling reactions, which result in the formation of a new C–C bond. Several strategies are known that enable α‐selective cross‐coupling of alkenyl gold complexes with aryl, allyl, or acyl coupling partners. We describe the direct β‐selective cross‐coupling of alkenyl gold complexes with simple alkyl electrophiles. We also describe the effects of the steric and electronic properties of alkenyl gold complexes on the selectivity of the cross‐coupling reaction. Abstract : Direct β‐selective alkylation of alkenyl gold complexes is achieved by using alkyl triflates as electrophiles. Steric and electronic properties of the alkenyl gold complexes are shown to affect both the selectivity and the reactivity. The observed selectivity to the alkylation reaction and the formation of cyclopropane‐containing by‐products suggest the presence of a gold carbene intermediate.