Gold‐Catalyzed Cyclizations of Alkynyl Silyl Enol Ethers: An Easy Access to Bicyclo[3.2.1]octanone Derivatives

Carrër, Amandine; Péan, Christophe; Perron-Sierra, Françoise; Mirguet, Olivier; Michelet, Véronique

doi:10.1002/adsc.201501135

Cited by 18 publications

(9 citation statements)

References 95 publications

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“…We initiated our study by investigating the reaction of enyne 1a , prepared from ethyl 4-oxocyclohexane carboxylate in a 3-step classical sequence, in the presence of different catalysts. The main results are summarized in Table .…”

Section: Resultsmentioning

confidence: 99%

“…Recently our groups have shown that cyclization reactions of alkynyl silyl enol ethers C were successfully applied to the preparation of bicyclo[3.2.1]octanone and bicyclo[3.3.1]nonanone derivatives D and E (Scheme , Eq. 2) . As part of our ongoing research program on the gold activation of alkynes leading to cycloisomerization as well as domino processes and our endeavor to access novel building blocks that would “escape from flatland”, we decided to study the unexplored gold-catalyzed cyclization of alkynyl cyclohexenyl of types F (Scheme , Eq.…”

Section: Introductionmentioning

confidence: 99%

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Gold-Catalyzed Cycloisomerization of 1,6-Cyclohexenylalkyne: An Efficient Entry to Bicyclo[3.2.1]oct-2-ene and Bicyclo[3.3.1]nonadiene

et al. 2020

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An efficient and mild synthetic route for the preparation of functionalized bicyclo[3.2.1]oct-2-ene and bicyclo[3.3.1]nonadiene via gold-mediated cycloisomerization of 1,6-enynes has been developed. This atom-economical catalytic process was optimized and relied on the efficiency of IPrAuNTf2 allowing the formation of functionalized bicyclic adducts in 55–91% isolated yields (18 products). The reliable access to bicyclic derivatives was demonstrated on a 3 g scale with a low catalyst loading. The process occurred on a 5-exo versus 6-endo pathway depending on the substitution of the alkynyl moiety. Density functional theory (DFT) calculations were performed on the stability of intermediates, and this study corroborated the endo/exo ratio and the mechanistic pathway with key intermediates. Reduction of the ester moiety and hydrogenation of the exo-methylene double bond of the bicyclo[3.2.1]oct-2-ene adduct illustrated the potential postfunctionalization of bicyclic derivatives.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Gold-Catalyzed Cycloisomerization of 1,6-Cyclohexenylalkyne: An Efficient Entry to Bicyclo[3.2.1]oct-2-ene and Bicyclo[3.3.1]nonadiene

et al. 2020

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“…Considering our endeavor for various types of goldcatalyzed cycloisomerization implying 1,6-enynes and leading potentially to bioactive molecules, we turned our attention towards an access to bicyclo[3.2.1]octanone derivatives, which are particularly interesting frameworks as they are subunit in many bioactive natural products. [15] Inspired by the pioneer work from Toste's and Nicolaou's groups [16] we decided to study the gold-catalyzed cyclization of alkynyl silyl enol ether (Table 1). The optimization showed a strong substrate and catalyst dependences.…”

Section: P E R S O N a L A C C O U N T T H E C H E M I C A L R E C O R Dmentioning

confidence: 99%

Gold‐Catalyzed Reactions Towards Diversity: From Simple Substrates to Functionalized Carbo‐ and Heterocycles

Michelet

2021

The Chemical Record

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The field of gold catalysis has been in constant expansion during the last twenty years. Based on the precept of π‐activation of unsaturated simple substrates, several new rearrangements have been discovered, implying aryl, alkyne, alkene or keto derivatives as key partners. In this personal account, the main contributions in the field of gold catalysis from our group will be highlighted, emphasizing the recent reports, starting from 1,6‐ and 1,5‐enynes and then moving to keto‐ynes derivatives. The gold‐catalyzed reactions will be presented starting from classical skeletal rearrangements (cycloisomerization) and then domino processes. In each part, the presentation of asymmetric versions will be highlighted.

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“…Some exceptions from acid-catalysis are included due to particular elegance of the transformation. Even though silyl enol ethers have been employed in a multitude of cyclisation procedures, [7] they will not be discussed within the scope of this survey. Cyclisations of chemically generated radical cations will as well be excluded.…”

Section: Introductionmentioning

confidence: 99%

Cyclisation Reactions Involving Alkyl Enol Ethers

2019

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Enol ethers are a fascinating product class and valuable building blocks with versatile reactivities and synthetic applications. With the emergence of silyl enol ethers, the chemistry of simple alkyl enol ethers has received less attention and targeted reviews of their chemistry are scarce. Especially intramolecular reactions under participation of an enol ether function have never been specifically surveyed. The construction of cyclic scaffolds is arguably one of the most important and challenging tasks of the organic chemist and intramolecular cyclisations represent the most straightforward tool to achieve this goal. The potential of enol ether-containing substrates to form oxygenated carbo-and heterocycles is obvious. The purpose of this review is to discuss their particular reactivity and to bring to the reader's attention how their unique properties have been harnessed by organic chemists for the construction of rings.

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Gold‐Catalyzed Cyclizations of Alkynyl Silyl Enol Ethers: An Easy Access to Bicyclo[3.2.1]octanone Derivatives

Cited by 18 publications

References 95 publications

Gold-Catalyzed Cycloisomerization of 1,6-Cyclohexenylalkyne: An Efficient Entry to Bicyclo[3.2.1]oct-2-ene and Bicyclo[3.3.1]nonadiene

Gold-Catalyzed Cycloisomerization of 1,6-Cyclohexenylalkyne: An Efficient Entry to Bicyclo[3.2.1]oct-2-ene and Bicyclo[3.3.1]nonadiene

Gold‐Catalyzed Reactions Towards Diversity: From Simple Substrates to Functionalized Carbo‐ and Heterocycles

Cyclisation Reactions Involving Alkyl Enol Ethers

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