Gold-Catalyzed Homo/Heterodimerization of Terminal Alkynes Facilitated by Metal-Ligand Cooperation

Overview

Journal Org Lett

Publisher American Chemical Society

Specialties Biochemistry
Chemistry

Date 2024 Jun 27

PMID 38935932

Authors

Xuan Wu

Liming Zhang

Affiliations

Soon will be listed here.

Abstract

Gold-catalyzed dimerization of terminal alkynes is achieved under mild reaction conditions and in excellent yields. In addition to homodimerizations, heterodimerizations between TBS acetylene and a range of terminal alkynes were realized using the syringe pump technique. The reaction tolerates various functional groups. The rate acceleration experienced in the reactions is enabled by metal-ligand cooperation. A binaphthyl-2-ylphosphine ligand featuring a 3'-diisopropylphosphoryl group plays a pivotal role in facilitating alkyne attack by accommodating and/or deprotonating its terminal proton.

References

Odabachian Y, Le Goff X, Gagosz F . An unusual access to medium sized cycloalkynes by a new gold(I)-catalysed cycloisomerisation of diynes. Chemistry. 2009; 15(36):8966-70. DOI: 10.1002/chem.200901312. View

Zuccarello G, Escofet I, Caniparoli U, Echavarren A . New-Generation Ligand Design for the Gold-Catalyzed Asymmetric Activation of Alkynes. Chempluschem. 2021; 86(9):1283-1296. PMC: 8457203. DOI: 10.1002/cplu.202100232. View

Wang Z, Wang Y, Zhang L . Soft propargylic deprotonation: designed ligand enables Au-catalyzed isomerization of alkynes to 1,3-dienes. J Am Chem Soc. 2014; 136(25):8887-90. PMC: 4089065. DOI: 10.1021/ja503909c. View

Wang Y, Wang Z, Li Y, Wu G, Cao Z, Zhang L . A general ligand design for gold catalysis allowing ligand-directed anti-nucleophilic attack of alkynes. Nat Commun. 2014; 5:3470. PMC: 4119785. DOI: 10.1038/ncomms4470. View

Grutzmacher H . Cooperating ligands in catalysis. Angew Chem Int Ed Engl. 2008; 47(10):1814-8. DOI: 10.1002/anie.200704654. View

Wei Y, Jiang J, Jing Y, Ke Z, Zhang L . Bifunctional Ligand Enables Gold-Catalyzed Propargyl C-H Functionalization via Reactive Gold Allenylidene Intermediate. Angew Chem Int Ed Engl. 2024; 63(29):e202402286. PMC: 11572476. DOI: 10.1002/anie.202402286. View

Wang Z, Nicolini C, Hervieu C, Wong Y, Zanoni G, Zhang L . Remote Cooperative Group Strategy Enables Ligands for Accelerative Asymmetric Gold Catalysis. J Am Chem Soc. 2017; 139(45):16064-16067. DOI: 10.1021/jacs.7b09136. View

Sun S, Kroll J, Luo Y, Zhang L . Gold-Catalyzed Regioselective Dimerization of Aliphatic Terminal Alkynes. Synlett. 2012; 2012(1):54-56. PMC: 3419542. DOI: 10.1055/s-0031-1289567. View

Zhang Y, Zhao K, Li X, Quintanilla C, Zhang L . Asymmetric Dearomatization of Phenols via Ligand-Enabled Cooperative Gold Catalysis. Angew Chem Int Ed Engl. 2023; 62(38):e202309256. PMC: 10528085. DOI: 10.1002/anie.202309256. View

10.

Jans A, Gomez-Suarez A, Nolan S, Reek J . A Switchable Gold Catalyst by Encapsulation in a Self-Assembled Cage. Chemistry. 2016; 22(42):14836-14839. PMC: 5053284. DOI: 10.1002/chem.201603162. View

11.

Gorin D, Sherry B, Toste F . Ligand effects in homogeneous Au catalysis. Chem Rev. 2008; 108(8):3351-78. PMC: 2754803. DOI: 10.1021/cr068430g. View

12.

Garcia-Fernandez P, Iglesias-Siguenza J, Rivero-Jerez P, Diez E, Gomez-Bengoa E, Fernandez R . Au-Catalyzed Hydroalkynylation of Haloalkynes. J Am Chem Soc. 2020; 142(37):16082-16089. DOI: 10.1021/jacs.0c07951. View

13.

Hashmi A . Dual gold catalysis. Acc Chem Res. 2014; 47(3):864-76. DOI: 10.1021/ar500015k. View

14.

Zhao K, Kohnke P, Yang Z, Cheng X, You S, Zhang L . Enantioselective Dearomative Cyclization Enabled by Asymmetric Cooperative Gold Catalysis. Angew Chem Int Ed Engl. 2022; 61(37):e202207518. DOI: 10.1002/anie.202207518. View

15.

Hashmi A, Lauterbach T, Nosel P, Vilhelmsen M, Rudolph M, Rominger F . Dual gold catalysis: σ,π-propyne acetylide and hydroxyl-bridged digold complexes as easy-to-prepare and easy-to-handle precatalysts. Chemistry. 2012; 19(3):1058-65. DOI: 10.1002/chem.201203010. View

16.

Khusnutdinova J, Milstein D . Metal-ligand cooperation. Angew Chem Int Ed Engl. 2015; 54(42):12236-73. DOI: 10.1002/anie.201503873. View

17.

Li X, Liao S, Wang Z, Zhang L . Ligand-Accelerated Gold-Catalyzed Addition of in Situ Generated Hydrazoic Acid to Alkynes under Neat Conditions. Org Lett. 2017; 19(14):3687-3690. DOI: 10.1021/acs.orglett.7b01359. View