Chloride-Tolerant Gold(I)-Catalyzed Regioselective Hydrochlorination of Alkynes

Overview

Journal ACS Catal

Publisher American Chemical Society

Date 2017 Oct 17

PMID 29034119

Citations 11

Authors

Rene Ebule

Shengzong Liang

Gerald B Hammond

Bo Xu

Affiliations

Soon will be listed here.

Abstract

We have developed a highly regioselective homogeneous gold(I)-catalyzed -hydrochlorination of unactivated alkynes at room temperature. We have overcome the incompatibility between conventional cationic gold catalysts and chloride by using a hydrogen-bonding activation of the Au-Cl bond. This approach is scalable, exhibits excellent functional group tolerance, and can be conducted in open air.

Citing Articles

Photoinduced Chloroamination Cyclization Cascade with -Chlorosuccinimide: From -(Allenyl)sulfonylamides to 2-(1-Chlorovinyl)pyrrolidines.

Azzi E, Ghigo G, Sarasino L, Parisotto S, Moro R, Renzi P J Org Chem. 2022; 88(10):6420-6433.

PMID: 36285672 PMC: 10204091. DOI: 10.1021/acs.joc.2c01963.

Regio- and stereoselective thiocyanatothiolation of alkynes and alkenes by using NHSCN and -thiosuccinimides.

Qi L, Liu S, Xiao L RSC Adv. 2022; 10(55):33450-33454.

PMID: 35515071 PMC: 9056709. DOI: 10.1039/d0ra06913b.

Decarbonylative Transfer Hydrochlorination of Alkenes and Alkynes Based on a B(C F ) -Initiated Grob Fragmentation.

Xie K, Oestreich M Angew Chem Int Ed Engl. 2022; 61(24):e202203692.

PMID: 35325506 PMC: 9321001. DOI: 10.1002/anie.202203692.

HCl•DMPU-Assisted One-pot and Metal-free Conversion of Aldehydes to Nitriles.

Mudshinge S, Potnis C, Xu B, Hammond G Green Chem. 2021; 22(13):4161-4164.

PMID: 33795972 PMC: 8009297. DOI: 10.1039/d0gc00757a.

Regio- and Stereoselective Synthesis of 1,2-Dihaloalkenes Using In-Situ-Generated ICl, IBr, BrCl, I2, and Br2.

Zeng X, Liu S, Yang Y, Yang Y, Hammond G, Xu B Chem. 2020; 6(4):1018-1031.

PMID: 32685767 PMC: 7367077. DOI: 10.1016/j.chempr.2020.03.011.

References

Zhu G, Chen D, Wang Y, Zheng R . Highly stereoselective synthesis of (Z)-1,2-dihaloalkenes by a Pd-catalyzed hydrohalogenation of alkynyl halides. Chem Commun (Camb). 2012; 48(46):5796-8. DOI: 10.1039/c2cc31553j. View

Jeschke P . The unique role of halogen substituents in the design of modern agrochemicals. Pest Manag Sci. 2009; 66(1):10-27. DOI: 10.1002/ps.1829. View

Hashmi A . Gold-catalyzed organic reactions. Chem Rev. 2007; 107(7):3180-211. DOI: 10.1021/cr000436x. View

Okoromoba O, Li Z, Robertson N, Mashuta M, Couto U, Tormena C . Achieving regio- and stereo-control in the fluorination of aziridines under acidic conditions. Chem Commun (Camb). 2016; 52(91):13353-13356. PMC: 5104567. DOI: 10.1039/c6cc07855a. View

Okoromoba O, Han J, Hammond G, Xu B . Designer HF-based fluorination reagent: highly regioselective synthesis of fluoroalkenes and gem-difluoromethylene compounds from alkynes. J Am Chem Soc. 2014; 136(41):14381-4. PMC: 4210154. DOI: 10.1021/ja508369z. View

Johnston P, Carthey N, Hutchings G . Discovery, Development, and Commercialization of Gold Catalysts for Acetylene Hydrochlorination. J Am Chem Soc. 2015; 137(46):14548-57. DOI: 10.1021/jacs.5b07752. View

Han F . Transition-metal-catalyzed Suzuki-Miyaura cross-coupling reactions: a remarkable advance from palladium to nickel catalysts. Chem Soc Rev. 2013; 42(12):5270-98. DOI: 10.1039/c3cs35521g. View

Lu Z, Kong W, Yuan Z, Zhao X, Zhu G . Synthesis of multisubstituted enamides via Pd-catalyzed chloroallylation of ynamides. J Org Chem. 2011; 76(20):8524-9. DOI: 10.1021/jo2015278. View

Kumar M, Hammond G, Xu B . Cationic gold catalyst poisoning and reactivation. Org Lett. 2014; 16(13):3452-5. PMC: 4084836. DOI: 10.1021/ol501663f. View

10.

Derien S, Klein H, Bruneau C . Selective ruthenium-catalyzed hydrochlorination of alkynes: one-step synthesis of vinylchlorides. Angew Chem Int Ed Engl. 2015; 54(41):12112-5. DOI: 10.1002/anie.201505144. View

11.

Iwai T, Fujihara T, Terao J, Tsuji Y . Iridium-catalyzed addition of acid chlorides to terminal alkynes. J Am Chem Soc. 2009; 131(19):6668-9. DOI: 10.1021/ja901778y. View

12.

Hartwig J . Evolution of a fourth generation catalyst for the amination and thioetherification of aryl halides. Acc Chem Res. 2008; 41(11):1534-44. PMC: 2819174. DOI: 10.1021/ar800098p. View

13.

Spaggiari A, Vaccari D, Davoli P, Torre G, Prati F . A mild synthesis of vinyl halides and gem-dihalides using triphenyl phosphite-halogen-based reagents. J Org Chem. 2007; 72(6):2216-9. DOI: 10.1021/jo061346g. View

14.

Derosa J, Cantu A, Boulous M, ODuill M, Turnbull J, Liu Z . Palladium(II)-Catalyzed Directed anti-Hydrochlorination of Unactivated Alkynes with HCl. J Am Chem Soc. 2017; 139(14):5183-5193. DOI: 10.1021/jacs.7b00892. View

15.

Lu Z, Han J, Hammond G, Xu B . Revisiting the Influence of Silver in Cationic Gold Catalysis: A Practical Guide. Org Lett. 2015; 17(18):4534-7. DOI: 10.1021/acs.orglett.5b02224. View

16.

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

17.

Su W, Jin C . First catalytic and green synthesis of aryl-(Z)-vinyl chlorides and its plausible addition-elimination mechanism. Org Lett. 2007; 9(6):993-6. DOI: 10.1021/ol062991c. View

18.

Hua R, Onozawa S, Tanaka M . Rhodium-catalyzed nondecarbonylative addition reaction of ClCOCOOC2H5 to alkynes. Chemistry. 2005; 11(12):3621-30. DOI: 10.1002/chem.200401279. View

19.

Hernandes M, Cavalcanti S, Moreira D, de Azevedo Junior W, Lima Leite A . Halogen atoms in the modern medicinal chemistry: hints for the drug design. Curr Drug Targets. 2010; 11(3):303-14. DOI: 10.2174/138945010790711996. View

20.

Wang B, Wang S, Li P, Wang L . Iron-catalyzed regio- and stereoselective addition of acid chlorides to alkynes. Chem Commun (Camb). 2010; 46(32):5891-3. DOI: 10.1039/c0cc01182g. View