Intermolecular gold(I)-catalyzed alkyne carboalkoxylation reactions for the multicomponent assembly of β-alkoxy ketones

Advanced Synthesis and Catalysis

Volumn 354, Issue 18, 2012, Pages 3451-3455

  Schultz, Danielle M ^a   Babij, Nicholas R ^a   Wolfe, John P ^a  

^a UNIVERSITY OF MICHIGAN   (United States)

Author keywords

aldehydes; alkynes; carbocations; gold; multicomponent reactions

Indexed keywords

EID: 84871091942     PISSN: 16154150     EISSN: 16154169     Source Type: Journal    
DOI: 10.1002/adsc.201200825     Document Type: Article

References (38)

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37. We cannot rule out the possibility that the nucleophilic species in these reactions are enol ethers (derived from hydroalkoxylation of the alkyne) rather than enols. However, we have not directly observed the formation of these species.
38. The lack of reactivity in the absence of the alkyne [Eq (2)] suggests that the alkyne may serve as a ligand for Au during one or more of the steps in this process. It is unclear why addition of 10 mol% alkyne failed to facilitate the Au-catalyzed reaction of 8 with 28. However, it is possible that at this low alkyne concentration the binding of alcohol or aldehyde to the Au-complex out-competes alkyne coordination (which is consistent with the observed poor reactivity when 10 equiv. of alcohol were employed in catalytic reactions). Under conditions of the catalytic reaction between 8 and 9 both the aldehyde and alcohol are consumed as the acetal intermediate is generated, which may minimize catalyst inhibition through this pathway.