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Intermolecular Gold(I)‐Catalyzed Alkyne Carboalkoxylation Reactions for the Multicomponent Assembly of β‐Alkoxy Ketones
dc.contributor.authorSchultz, Danielle M.en_US
dc.contributor.authorBabij, Nicholas R.en_US
dc.contributor.authorWolfe, John P.en_US
dc.date.accessioned2013-01-03T19:35:18Z
dc.date.available2014-01-07T14:51:07Zen_US
dc.date.issued2012-12-14en_US
dc.identifier.citationSchultz, Danielle M.; Babij, Nicholas R.; Wolfe, John P. (2012). "Intermolecular Gold(I)‐Catalyzed Alkyne Carboalkoxylation Reactions for the Multicomponent Assembly of β‐Alkoxy Ketones." Advanced Synthesis & Catalysis 354(18): 3451-3455. <http://hdl.handle.net/2027.42/94667>en_US
dc.identifier.issn1615-4150en_US
dc.identifier.issn1615-4169en_US
dc.identifier.urihttps://hdl.handle.net/2027.42/94667
dc.description.abstractA new gold(I)‐catalyzed multicomponent synthesis of β‐alkoxy ketones from aldehydes, alcohols, and alkynes is described. This atom economical synthesis was achieved through the use of the gold complex (SPhos)AuNTf 2 as a catalyst, and allows for the preparation of a diverse array of β‐alkoxy ketone products. Mechanistic studies illustrate that these reactions proceed via gold(I)‐catalyzed hydrolysis of the alkyne to an aryl ketone, which then undergoes an aldol reaction with an oxocarbenium ion generated in situ from the aldehyde and alcohol components.en_US
dc.publisherWILEY‐VCH Verlagen_US
dc.subject.otherGolden_US
dc.subject.otherAlkynesen_US
dc.subject.otherAldehydesen_US
dc.subject.otherCarbocationsen_US
dc.subject.otherMulticomponent Reactionsen_US
dc.titleIntermolecular Gold(I)‐Catalyzed Alkyne Carboalkoxylation Reactions for the Multicomponent Assembly of β‐Alkoxy Ketonesen_US
dc.typeArticleen_US
dc.rights.robotsIndexNoFollowen_US
dc.subject.hlbsecondlevelChemistryen_US
dc.subject.hlbtoplevelScienceen_US
dc.description.peerreviewedPeer Revieweden_US
dc.contributor.affiliationumDepartment of Chemistry, University of Michigan, 930 N. University Ave., Ann Arbor, MI 48109‐1055, USAen_US
dc.contributor.affiliationumDepartment of Chemistry, University of Michigan, 930 N. University Ave., Ann Arbor, MI 48109‐1055, USAen_US
dc.description.bitstreamurlhttp://deepblue.lib.umich.edu/bitstream/2027.42/94667/1/adsc_201200825_sm_miscellaneous_information.pdf
dc.description.bitstreamurlhttp://deepblue.lib.umich.edu/bitstream/2027.42/94667/2/3451_ftp.pdf
dc.identifier.doi10.1002/adsc.201200825en_US
dc.identifier.sourceAdvanced Synthesis & Catalysisen_US
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dc.identifier.citedreferenceThe reactions described in this paper do not appear to be air‐sensitive, and use of rigorously anhydrous conditions is not required. All alcohols and alkynes were used as obtained from commercial sources, without drying, distillation, or purification by other means.en_US
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dc.identifier.citedreferenceAddition of 10 mol% 9 to this reaction mixture also led to no observed reactivity.en_US
dc.identifier.citedreferenceAt no time was the formation of the corresponding β‐hydroxy ketone product 34 observed.en_US
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dc.identifier.citedreferenceTreatment of 34 with SPhosAuNTf 2, phenylacetylene, and MeOH in CH 2 Cl 2 for 16 h led to ca. 45% conversion to 10, whereas the catalytic reaction between 8 and 9 to yield 10 was complete in 8 h.en_US
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dc.identifier.citedreferenceWe 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.en_US
dc.identifier.citedreferenceThe 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.en_US
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dc.owningcollnameInterdisciplinary and Peer-Reviewed


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