Gold-catalyzed Propargylic Substitutions: Scope and Synthetic Developments

Overview

Journal Beilstein J Org Chem

Specialty Chemistry

Date 2011 Aug 2

PMID 21804883

Citations 2

Authors

Olivier Debleds

Eric Gayon

Emmanuel Vrancken

Jean-Marc Campagne

Affiliations

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Abstract

This personal account summarizes our recent developments in gold-catalyzed direct substitutions on propargylic (allylic, benzylic) alcohols, with various nucleophiles (and bi-nucleophiles) based on the σ- and/or π-acidity of gold(III) complexes. Synthetic developments are also briefly described.

Citing Articles

Scope and advances in the catalytic propargylic substitution reaction.

Roy R, Saha S RSC Adv. 2022; 8(54):31129-31193.

PMID: 35548716 PMC: 9085608. DOI: 10.1039/c8ra04481c.

Tunable Gold-catalyzed Reactions of Propargyl Alcohols and Aryl Nucleophiles.

Jonsson H, Solvi T, Lomeland S, Reiersolmoen A, Fiksdahl A ChemistryOpen. 2022; 11(5):e202200030.

PMID: 35274479 PMC: 9059295. DOI: 10.1002/open.202200030.

References

Corma A, Leyva-Perez A, Sabater M . Gold-catalyzed carbon-heteroatom bond-forming reactions. Chem Rev. 2011; 111(3):1657-712. DOI: 10.1021/cr100414u. View

Zhan Z, Yu J, Liu H, Cui Y, Yang R, Yang W . A general and efficient FeCl3-catalyzed nucleophilic substitution of propargylic alcohols. J Org Chem. 2006; 71(21):8298-301. DOI: 10.1021/jo061234p. View

Cozzi P, Benfatti F . Stereoselective reactions with stabilized carbocations. Angew Chem Int Ed Engl. 2009; 49(2):256-9. DOI: 10.1002/anie.200905235. View

Matsuzawa H, Miyake Y, Nishibayashi Y . Ruthenium-catalyzed enantioselective propargylation of aromatic compounds with propargylic alcohols via allenylidene intermediates. Angew Chem Int Ed Engl. 2007; 46(34):6488-91. DOI: 10.1002/anie.200701261. View

Pennell M, Unthank M, Turner P, Sheppard T . A general procedure for the synthesis of enones via gold-catalyzed Meyer-Schuster rearrangement of propargylic alcohols at room temperature. J Org Chem. 2011; 76(5):1479-82. DOI: 10.1021/jo102263t. View

Debleds O, Campagne J . 1,5-Enyne metathesis. J Am Chem Soc. 2008; 130(5):1562-3. DOI: 10.1021/ja0780986. View

Debleds O, Gayon E, Ostaszuk E, Vrancken E, Campagne J . A versatile iron-catalyzed protocol for the one-pot synthesis of isoxazoles or isoxazolines from the same propargylic alcohols. Chemistry. 2010; 16(40):12207-13. DOI: 10.1002/chem.201001461. View

Cuenca A, Mancha G, Asensio G, Medio-Simon M . Water compatible gold(III)-catalysed synthesis of unsymmetrical ethers from alcohols. Chemistry. 2007; 14(5):1518-23. DOI: 10.1002/chem.200701134. View

Kuninobu Y, Ishii E, Takai K . Rhenium- and gold-catalyzed coupling of aromatic aldehydes with trimethyl(phenylethynyl)silane: synthesis of diethynylmethanes. Angew Chem Int Ed Engl. 2007; 46(18):3296-9. DOI: 10.1002/anie.200700183. View

10.

Blanc A, Tenbrink K, Weibel J, Pale P . Mechanistic studies and improvement of coinage metal-catalyzed transformation of alkynyloxiranes to furans: an alcohol addition-cyclization-elimination cascade. J Org Chem. 2009; 74(15):5342-8. DOI: 10.1021/jo9008172. View

11.

Wang W, Xu B, Hammond G . Efficient synthesis of gamma-keto esters through neighboring carbonyl group-assisted regioselective hydration of 3-alkynoates. J Org Chem. 2009; 74(4):1640-3. DOI: 10.1021/jo802450n. View

12.

Cordonnier M, Blanc A, Pale P . Gold(I)-catalyzed rearrangement of alkynyloxiranes: a mild access to divinyl ketones. Org Lett. 2008; 10(8):1569-72. DOI: 10.1021/ol800219k. View

13.

Ohri R, Radosevich A, Hrovat K, Musich C, Huang D, Holman T . A Re(V)-catalyzed C-N bond-forming route to human lipoxygenase inhibitors. Org Lett. 2005; 7(12):2501-4. DOI: 10.1021/ol050897a. View

14.

Rao W, Chan P . Gold-catalysed allylic alkylation of aromatic and heteroaromatic compounds with allylic alcohols. Org Biomol Chem. 2008; 6(13):2426-33. DOI: 10.1039/b805067h. View

15.

Aponick A, Li C, Malinge J, Marques E . An extremely facile synthesis of furans, pyrroles, and thiophenes by the dehydrative cyclization of propargyl alcohols. Org Lett. 2009; 11(20):4624-7. DOI: 10.1021/ol901901m. View

16.

Lee K, Lee P . Efficient synthetic method of multisubstituted allenes from the reactions of allylindium reagents with 3 degree-propargyl alcohols. Org Lett. 2008; 10(12):2441-4. DOI: 10.1021/ol800719g. View

17.

Gayon E, Debleds O, Nicouleau M, Lamaty F, van der Lee A, Vrancken E . Highly diastereoselective Baldwin rearrangement of isoxazolines into cis-acylaziridines. J Org Chem. 2010; 75(17):6050-3. DOI: 10.1021/jo101273d. View

18.

Bandini M, Tragni M . Pi-activated alcohols: an emerging class of alkylating agents for catalytic Friedel-Crafts reactions. Org Biomol Chem. 2009; 7(8):1501-7. DOI: 10.1039/b823217b. View

19.

Li Z, Brouwer C, He C . Gold-catalyzed organic transformations. Chem Rev. 2008; 108(8):3239-65. DOI: 10.1021/cr068434l. View

20.

Detz R, Delville M, Hiemstra H, van Maarseveen J . Enantioselective copper-catalyzed propargylic amination. Angew Chem Int Ed Engl. 2008; 47(20):3777-80. DOI: 10.1002/anie.200705264. View