Ambient gold-catalyzed <i>O</i>-vinylation of cyclic 1,3-diketone: A vinyl ether synthesis

Xi, Yumeng; Dong, Boliang; Shi, Xiaodong

doi:10.3762/bjoc.9.288

Cited by 12 publications

(3 citation statements)

References 31 publications

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“…Since the two-fold addition of alcohols to mono-alkynes is the common mode of reactivity observed, [43][44] this opens up a facile synthetic route to di(vinyl ethers), which are usually challenging to synthesize by gold catalysis. [45][46][47][48][49] Since the reactivity of 1,3-butadiynes in gold catalysis has only rarely been subjected mechanistically, [22,[50][51] special attention has now been paid to mechanistic details, including kinetic and computational studies.…”

Section: Introductionmentioning

confidence: 99%

“…In contrast to this observation, here we present the first gold‐catalyzed intermolecular functionalization of 1,3‐butadiynes by two nucleophiles to selectively give 1,3‐butadienes. Since the two‐fold addition of alcohols to mono‐alkynes is the common mode of reactivity observed, [43–44] this opens up a facile synthetic route to di(vinyl ethers), which are usually challenging to synthesize by gold catalysis [45–49] …”

Section: Introductionmentioning

confidence: 99%

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Gold Catalysis: 2,3‐ or 1,4‐Addition to Butadiynes

Stein¹,

Pascher²,

Stracke³

et al. 2022

Adv Synth Catal

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In the past, numerous impressive methodologies have been developed in homogeneous gold catalysis, typically using alkynes, allenes, or different non‐conjugated diyne systems as starting materials. While there are applications catalyzed by other transition metals, the use of 1,3‐butadiyne derivatives has been largely neglected in gold catalysis. In this work we present an efficient gold‐catalyzed method focusing on the functionalization of this specific type of diynes. The starting materials can be synthesized via simple Glaser Coupling, starting from cheap, highly variable, terminal alkynes. These homocoupling products, which are often observed as undesirable side‐products in Sonogashira reactions, can be converted into versatile 1,3‐butadiene derivatives in alcohol as a solvent and nucleophile under mild conditions. The possible field of application of the 1,3‐butadiene derivatives known from the literature is very broad and ranges from a use as transistor or OLED material to a use as an enzyme inhibitor. The approach presented here offers an attractive and highly effective way to versatile functionalized 1,3‐butadiene derivatives.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Gold Catalysis: 2,3‐ or 1,4‐Addition to Butadiynes

Stein¹,

Pascher²,

Stracke³

et al. 2022

Adv Synth Catal

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“…However, noncyclic 1,3-ketones already failed to give the desired oxygen addition. [25] We envisioned av inyl ether synthesis accessible by simple startingm aterials under mild conditions by exploiting the aforementioned aurated carbocationic intermediates insteado f alkynes as electrophiles and simple ketonesi nsteado fa lcohols or 1,3-ketones as nucleophiles. Due to the high reactivity of these speciesakinetic control of the reaction should be feasible preferring the attack of the carbonyl oxygen insteado ft he enol carbon of the respective tautomer,w hich is only available in very low concentrations in the reaction mixture.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Fulvene Vinyl Ethers by Gold Catalysis

Ahrens

Schwarz

Lustosa

et al. 2020

Chemistry A European J

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Gold-catalyzed cyclization of 1,5-diynesw ith ketones as reagents and solvent provides diversely substituted vinyl ethers under mild conditions. The regioselectivity of such gold-catalyzed cyclizations is usually controlled by the scaffold of the diyne. Herein, we report the first solvent-controlled switchingo fr egioselectivity from a6 -endo-dig-to 5endo-dig-cyclization in these transformations,p roviding fulvene derivatives. With respectt ot he functional-group toler-ance, aryl fluorides, chlorides, bromides,and ethers are tolerated. Furthermore, the mechanism and selectivity are put to scrutinyb ye xperimental studies and at hermodynamic analysis of the product. Additionally,6 -(vinyloxy)fulvenesa re a hitherto unknown class of compounds. Theirr eactivity is briefly evaluated, to give insights into their potential applications.[ + + ] Crystallographic investigation;T heoreticali nvestigation Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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Gold‐Catalyzed Addition ofHXto Alkynes

Genin

Michelet

2014

Patai's Chemistry of Functional Groups

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Among the myriad of organic transformations that have been developed in the area of gold catalysis, the addition of HX to alkynes has been a field of intense investigation. This chapter presents the main and recent contributions in the field of gold‐catalyzed nucleophilic addition of HX to alkynes. The presentation includes the addition of O ‐nucleophiles (including water, alcohols and carboxylic acids), of N ‐nucleophiles and other heteroatom nucleophiles (including thiols and halogens) to alkynes. The historical background for inter‐ and intramolecular additions, the domino processes and the applications to natural products synthesis are highlighted.

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Ambient gold-catalyzed O-vinylation of cyclic 1,3-diketone: A vinyl ether synthesis

Cited by 12 publications

References 31 publications

Gold Catalysis: 2,3‐ or 1,4‐Addition to Butadiynes

Gold Catalysis: 2,3‐ or 1,4‐Addition to Butadiynes

Synthesis of Fulvene Vinyl Ethers by Gold Catalysis

Gold‐Catalyzed Addition ofHXto Alkynes

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