Tandem Au-Catalyzed 3,3-Rearrangement−[2 + 2] Cycloadditions of Propargylic Esters:  Expeditious Access to Highly Functionalized 2,3-Indoline-Fused Cyclobutanes

Zhang, Liming

doi:10.1021/ja056419c

Cited by 450 publications

(179 citation statements)

References 19 publications

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“…[36] We have established ), which, taking into consideration the possible experimental error, renders both pathways competitive. Therefore, in an effort to try to understand every aspect of the cyclization studied here, and willing to consider thoroughly any possibility, we carried out labeling experiments with 2-18 O, our model substrate with a carbonyl oxygen atom 47 % enriched in 18 O, to address this issue.…”

Section: O-labeling Experimentsmentioning

confidence: 96%

Gold‐ and Platinum‐Catalyzed Cycloisomerization of Enynyl Esters versus Allenenyl Esters: An Experimental and Theoretical Study

Marion

Lemière

Correa

et al. 2009

Chemistry A European J

130

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Ester-way to heaven: Unexpected formation of bicyclo[3.1.0]hexene 4 was the main focus of combined experimental and theoretical studies on the Au-catalyzed cycloisomerization of branched dienyne 1 (see scheme), which provided better understanding of the mechanistic details governing the cyclization of enynes bearing a propargylic ester group.Experimental and theoretical studies on Au- and Pt-catalyzed cycloisomerization of a branched dienyne with an acetate group at the propargylic position are presented. The peculiar architecture of the dienyne precursor, which has both a 1,6- and a 1,5-enyne skeleton, leads, in the presence of alkynophilic gold catalysts, to mixtures of bicyclic compounds 3, 4, and 5. Formation of unprecedented bicyclo[3.1.0]hexene 5 is the main focus of this study. The effect of the ancillary ligand on the gold center was examined and found to be crucial for formation of 5. Further mechanistic studies, involving cyclization of an enantioenriched dienyne precursor, (18)O-labeling experiments, and DFT calculations, allowed an unprecedented reaction pathway to be proposed. We show that bicyclo[3.1.0]hexene 5 is likely formed by a 1,3-OAc shift/allene-ene cyclization/1,2-OAc shift sequence, as calculated by DFT and supported by Au-catalyzed cyclization of isolated allenenyl acetate 7, which leads to improved selectivity in the formation of 5. Additionally, the possibility of OAc migration from allenyl acetates was supported by a trapping experiment with styrene that afforded the corresponding cyclopropane derivative. This unprecedented generation of a vinyl metal carbene from an allenyl ester supports a facile enynyl ester/allenenyl ester equilibrium. Further examination of the difference in reactivity between enynyl acetates and their corresponding [3,3]-rearranged allenenyl acetates toward Au- and Pt-catalyzed cycloisomerization is also presented.

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Section: O-labeling Experimentsmentioning

confidence: 96%

Gold‐ and Platinum‐Catalyzed Cycloisomerization of Enynyl Esters versus Allenenyl Esters: An Experimental and Theoretical Study

Marion

Lemière

Correa

et al. 2009

Chemistry A European J

130

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“…13 It was proposed that the catalyst played dual role for activating both propargylic esters and the in situ generated allenylic esters. …”

Section: Methodsmentioning

confidence: 99%

Gold-catalyzed reactions of oxo-alkynes

Patil¹,

Yamamoto²

2006

Arkivoc

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“…Ein Wechsel zu CH 3 [11] dieser Reaktion schlagen wir die in Schema 2 gezeigte Sequenz vor. Das Propargylpivalat 1 geht eine Au I -katalysierte 1,3-AcyloxyVerschiebung [12] zur Au I -Oxocarbenium-Zwischenstufe A ein. [13] Nach der Hydrolyse der Zwischenstufe A wird der Au IKomplex B gebildet.…”

Section: Auunclassified

Dehydrierende Meyer‐Schuster‐Umlagerung: Gold‐katalysierte Synthese von Alkinen

Yang

Pflästerer

et al. 2013

Angewandte Chemie

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Leicht zugängliche Propargylester werden durch eine oxidative Gold-katalysierte Reaktion in die invertierten Alkinylketone überführt. Der Gagosz-Katalysator in Kombination mit PhI(OAc) 2 erweist sich als das beste System für diese Umwandlung, und 18 Beispiele mit Ausbeuten bis zu 80 % werden beschrieben. Die Ergebnisse lassen darauf schließen, dass die Dreifachbindung im Produkt durch Eliminierung aus einer Vinylgold-Zwischenstufe entsteht. Formal ist diese neue Reaktion eine dehydrierende Meyer-SchusterUmlagerung.

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Tandem Au-Catalyzed 3,3-Rearrangement−[2 + 2] Cycloadditions of Propargylic Esters: Expeditious Access to Highly Functionalized 2,3-Indoline-Fused Cyclobutanes

Cited by 450 publications

References 19 publications

Gold‐ and Platinum‐Catalyzed Cycloisomerization of Enynyl Esters versus Allenenyl Esters: An Experimental and Theoretical Study

Gold‐ and Platinum‐Catalyzed Cycloisomerization of Enynyl Esters versus Allenenyl Esters: An Experimental and Theoretical Study

Gold-catalyzed reactions of oxo-alkynes

Dehydrierende Meyer‐Schuster‐Umlagerung: Gold‐katalysierte Synthese von Alkinen

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