Reactivity of Stabilized Vinyldiazo Compounds toward Alkenyl- and Alkynylsilanes under Gold Catalysis: Regio- and Stereoselective Synthesis of Skipped Dienes and Enynes

Bernardo, Olaya; Yamamoto, Kota; Fernández, Israel; López, Luís A.

doi:10.1021/acs.orglett.1c01381

Cited by 9 publications

(7 citation statements)

References 23 publications

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“…Inspired by Hashmi's elegant work and as part of our on‐going interest in the reactivity of gold vinylcarbene precursors toward unsaturated organosilicon reagents, [9] we became interested in exploring the behavior of propargyl esters toward alkynylsilanes under gold catalysis. We hypothesized that the bulkiness of the silyl group in the alkynylsilane, which might hinder a cyclization reaction, together with the ability of the C‐Si σ‐bond to stabilize an adjacent carbocation (the so‐called β‐silicon effect), [10] could provide a favorable scenario for alternative pathways.…”

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confidence: 99%

Gold‐Catalyzed Reaction of Propargyl Esters and Alkynylsilanes: Synthesis of Vinylallene Derivatives through a Twofold 1,2‐Rearrangement

et al. 2021

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The reaction of propargyl esters with alkynylsilanes under gold catalysis provides vinylallene derivatives through consecutive [1,2]‐acyloxy/[1,2]‐silyl rearrangements. Good yields, full atom‐economy, broad substrate scope, easy scale‐up and low catalyst loadings are salient features of this novel transformation. Density Functional Theory (DFT) calculations suggest a reaction mechanism involving initial [1,2]‐acyloxy rearrangement to generate a gold vinylcarbene intermediate which upon regioselective attack of the alkynylsilane affords a vinyl cation which undergoes a type II‐dyotropic rearrangement involving the silyl group and the metal fragment. Preliminary results on the enantioselective version of this transformation are also disclosed.

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confidence: 99%

Gold‐Catalyzed Reaction of Propargyl Esters and Alkynylsilanes: Synthesis of Vinylallene Derivatives through a Twofold 1,2‐Rearrangement

et al. 2021

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“…Additionally, the major formation of the acyclic product 4 when cyclopentanone‐derived silyl enol ether 2 k was used can also confirm the preference for oxonium intermediates B’ (Scheme 6 ) Thus, silyl oxonium intermediate B ’ can evolve to the [4+2] cycloaddition product 3 , or through an alternative pathway, involving silyldeauration, [24] leading to vinyl silane E that in the work up conditions would undergo protodesilylation and double bond isomerization to give the acyclic cyclopentanone derivative 4 .…”

Section: Resultsmentioning

confidence: 82%

Gold(I)‐Catalyzed Intermolecular Formal [4+2] Cycloaddition of O‐Aryl Ynol Ethers and Enol Ethers: Synthesis of Chromene Derivatives

Suárez-Rodríguez

Suárez‐Sobrino

Ballesteros

2021

Chemistry A European J

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Gold(I)-catalyzed formal [4 + 2] cycloaddition of Oaryl ynol ethers 1 and enol ethers 2 is described. This intermolecular reaction between two electron-rich unsaturated systems takes place, under mild conditions, in the presence of 5 mol% [IPrAu(CH 3 CN)]SbF 6 as catalyst giving chromene derivatives with good yields. The cycloaddition is completely regio-and stereoselective, as well as versatile for both reactives. Silyl enol ethers can also react in the same way and under the same reaction conditions with quantitative yields. A plausible mechanism through a selective addition of the enol ether to the alkyne gold activated complex followed by an intramolecular aromatic electrophilic substitution is proposed. Several experimental results support the presence of a cationic oxonium intermediate prior to the aromatic substitution. The reaction represents a new entry to the chromene core.

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“…More recently, while exploring the reactivity of vinyldiazo compounds towards vinylsilanes under gold catalysis (see Section 2.1, Scheme 8), 17 we evaluated alkynylsilanes as reaction partners.…”

Section: Gold-catalyzed Reactions Of Vinyldiazo Compounds With Alkynesmentioning

confidence: 99%

Recent Advances in Gold-Catalyzed Transformations of Vinyldiazo Reagents

López,

Bernardo,

García-Martínez

et al. 2024

Synthesis

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Since their discovery in 2011, gold-catalyzed transformations of vinyldiazo compounds have become an important synthetic tool, enabling the identification of new reaction patterns that have greatly expanded the versatility of these reagents. In this short review, we showcase the most relevant advances that have been made in this exciting area of research.1 Introduction2 Gold-Catalyzed Transformations of Vinyldiazo Compounds Involving Metal Carbene Intermediates2.1 Liu’s Seminal Work: Vinylogous Reactivity of Au(I) Vinyl Carbenes2.2 Gold-Catalyzed Reactions of Vinyldiazo Compounds with Alkenes2.3 Gold-Catalyzed Reactions of Vinyldiazo Compounds with Alkynes2.4 Gold-Catalyzed Reactions of Vinyldiazo Compounds with Allenes2.5 Gold-Catalyzed Reactions of Vinyldiazo Reagents with Aromatic Compounds2.6 Gold-Catalyzed Reactions of Vinyldiazo Compounds with Nitriles2.7 Gold-Catalyzed Diazo Cross-Couplings3 Gold-Catalyzed Transformations of Vinyldiazo Compounds That Do Not Involve Initial Dinitrogen Extrusion3.1 Gold-Catalyzed Formal [n+2] Cycloaddition Reactions through the Vinyl Moiety of Vinyldiazo Compounds3.2 Gold-Catalyzed Transformations of Vinyldiazo Compounds Involving Initial Activation of the Non-Diazo Reagent4 Conclusions

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Reactivity of Stabilized Vinyldiazo Compounds toward Alkenyl- and Alkynylsilanes under Gold Catalysis: Regio- and Stereoselective Synthesis of Skipped Dienes and Enynes

Cited by 9 publications

References 23 publications

Gold‐Catalyzed Reaction of Propargyl Esters and Alkynylsilanes: Synthesis of Vinylallene Derivatives through a Twofold 1,2‐Rearrangement

Gold‐Catalyzed Reaction of Propargyl Esters and Alkynylsilanes: Synthesis of Vinylallene Derivatives through a Twofold 1,2‐Rearrangement

Gold(I)‐Catalyzed Intermolecular Formal [4+2] Cycloaddition of O‐Aryl Ynol Ethers and Enol Ethers: Synthesis of Chromene Derivatives

Recent Advances in Gold-Catalyzed Transformations of Vinyldiazo Reagents

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