Metal-Free C-H Borylation of N-Heteroarenes by Boron Trifluoride

Overview

Journal Chemistry

Specialty Chemistry

Date 2020 Jun 2

PMID 32478432

Citations 8

Authors

Vladimir Iashin

Denes Berta

Konstantin Chernichenko

Martin Nieger

Karina Moslova

Imre Papai

Timo Repo

Affiliations

Soon will be listed here.

Abstract

Organoboron compounds are essential reagents in modern C-C coupling reactions. Their synthesis via catalytic C-H borylation by main group elements is emerging as a powerful tool alternative to transition metal based catalysis. Herein, a straightforward metal-free synthesis of aryldifluoroboranes from BF and heteroarenes is reported. The reaction is assisted by sterically hindered amines and catalytic amounts of thioureas. According to computational studies the reaction proceeds via frustrated Lewis pair (FLP) mechanism. The obtained aryldifluoroboranes are further stabilized against destructive protodeborylation by converting them to the corresponding air stable tetramethylammonium organotrifluoroborates.

Citing Articles

1-Butyl-3-methylimidazolium tetrafluoroborate as suitable solvent for BF: the case of alkyne hydration. Chemistry vs electrochemistry.

David M, Galli E, Brown R, Feroci M, Vetica F, Bortolami M Beilstein J Org Chem. 2024; 19:1966-1981.

PMID: 38169890 PMC: 10760484. DOI: 10.3762/bjoc.19.147.

Metal-free C-H Borylation and Hydroboration of Indoles.

Nad P, Mukherjee A ACS Omega. 2023; 8(41):37623-37640.

PMID: 37867714 PMC: 10586279. DOI: 10.1021/acsomega.3c05071.

Main Group Catalyzed Arene Borylation: Challenges and Opportunities.

Ingleson M ACS Catal. 2023; 13(11):7691-7697.

PMID: 37288098 PMC: 10242676. DOI: 10.1021/acscatal.3c01668.

Thioacetalation and Multi-Component Thiomethylative Friedel-Crafts Arylation Using BFSMe.

Soderstrom M, Matt C, Odell L ACS Omega. 2023; 8(4):4320-4330.

PMID: 36743056 PMC: 9893757. DOI: 10.1021/acsomega.2c07608.

Synthesis of cis-thiiranes as diastereoselective access to epoxide congeners via 4π-electrocyclization of thiocarbonyl ylides.

Song S, Jin J, Choi J, Chung W Nat Commun. 2022; 13(1):4818.

PMID: 35974103 PMC: 9381720. DOI: 10.1038/s41467-022-32499-3.

References

Wang G, Xu L, Li P . Double N,B-Type Bidentate Boryl Ligands Enabling a Highly Active Iridium Catalyst for C-H Borylation. J Am Chem Soc. 2015; 137(25):8058-61. DOI: 10.1021/jacs.5b05252. View

Fontaine F, Rochette E . Ambiphilic Molecules: From Organometallic Curiosity to Metal-Free Catalysts. Acc Chem Res. 2018; 51(2):454-464. DOI: 10.1021/acs.accounts.7b00514. View

Ishida N, Moriya T, Goya T, Murakami M . Synthesis of pyridine-borane complexes via electrophilic aromatic borylation. J Org Chem. 2010; 75(24):8709-12. DOI: 10.1021/jo101920p. View

Lennox A, Lloyd-Jones G . Preparation of organotrifluoroborate salts: precipitation-driven equilibrium under non-etching conditions. Angew Chem Int Ed Engl. 2012; 51(37):9385-8. DOI: 10.1002/anie.201203930. View

Shih J, Nguyen T, May J . Organocatalyzed Asymmetric Conjugate Addition of Heteroaryl and Aryl Trifluoroborates: a Synthetic Strategy for Discoipyrrole D. Angew Chem Int Ed Engl. 2015; 54(34):9931-5. DOI: 10.1002/anie.201503528. View

Del Grosso A, Singleton P, Muryn C, Ingleson M . Pinacol boronates by direct arene borylation with borenium cations. Angew Chem Int Ed Engl. 2011; 50(9):2102-6. DOI: 10.1002/anie.201006196. View

Chernichenko K, Kotai B, Papai I, Zhivonitko V, Nieger M, Leskela M . Intramolecular frustrated Lewis pair with the smallest boryl site: reversible H2 addition and kinetic analysis. Angew Chem Int Ed Engl. 2014; 54(6):1749-53. DOI: 10.1002/anie.201410141. View

Chernichenko K, Madarasz A, Papai I, Nieger M, Leskela M, Repo T . A frustrated-Lewis-pair approach to catalytic reduction of alkynes to cis-alkenes. Nat Chem. 2013; 5(8):718-23. DOI: 10.1038/nchem.1693. View

Lindqvist M, Borre K, Axenov K, Kotai B, Nieger M, Leskela M . Chiral molecular tweezers: synthesis and reactivity in asymmetric hydrogenation. J Am Chem Soc. 2015; 137(12):4038-41. DOI: 10.1021/ja512658m. View

10.

Iqbal S, Cid J, Procter R, Uzelac M, Yuan K, Ingleson M . Acyl-Directed ortho-Borylation of Anilines and C7 Borylation of Indoles using just BBr. Angew Chem Int Ed Engl. 2019; 58(43):15381-15385. PMC: 6856876. DOI: 10.1002/anie.201909786. View

11.

Crossley D, Cid J, Curless L, Turner M, Ingleson M . Facile Arylation of Four-Coordinate Boron Halides by Borenium Cation Mediated Boro-desilylation and -destannylation. Organometallics. 2016; 34(24):5767-5774. PMC: 4819459. DOI: 10.1021/acs.organomet.5b00857. View

12.

Chernichenko K, Lindqvist M, Kotai B, Nieger M, Sorochkina K, Papai I . Metal-Free sp(2)-C-H Borylation as a Common Reactivity Pattern of Frustrated 2-Aminophenylboranes. J Am Chem Soc. 2016; 138(14):4860-8. DOI: 10.1021/jacs.6b00819. View

13.

Chernichenko K, Kotai B, Nieger M, Heikkinen S, Papai I, Repo T . Replacing CF groups with Cl and H atoms in frustrated Lewis pairs: H additions and catalytic hydrogenations. Dalton Trans. 2017; 46(7):2263-2269. DOI: 10.1039/c6dt04649e. View

14.

Del Grosso A, Helm M, Solomon S, Caras-Quintero D, Ingleson M . Simple inexpensive boron electrophiles for direct arene borylation. Chem Commun (Camb). 2011; 47(46):12459-61. DOI: 10.1039/c1cc14226g. View

15.

Yin Q, Klare H, Oestreich M . Catalytic Friedel-Crafts C-H Borylation of Electron-Rich Arenes: Dramatic Rate Acceleration by Added Alkenes. Angew Chem Int Ed Engl. 2017; 56(13):3712-3717. DOI: 10.1002/anie.201611536. View

16.

Roscales S, Csaky A . Metal-free ring-opening of epoxides with potassium trifluoroborates. Chem Commun (Camb). 2013; 50(4):454-6. DOI: 10.1039/c3cc47360k. View

17.

Brady P, Carreira E . Addition of Trifluoroborates to Oxetanyl N,O-Acetals: Entry into Spiro and Fused Saturated Heterocycles. Org Lett. 2015; 17(13):3350-3. DOI: 10.1021/acs.orglett.5b01607. View

18.

Vieira A, Fiorante P, Hough T, Ferreira F, Ludtke D, Stefani H . Nucleophilic addition of potassium alkynyltrifluoroborates to D-glucal mediated by BF3 x OEt2: highly stereoselective synthesis of alpha-C-glycosides. Org Lett. 2008; 10(22):5215-8. DOI: 10.1021/ol8022177. View

19.

Stephan D . Frustrated Lewis pairs: from concept to catalysis. Acc Chem Res. 2014; 48(2):306-16. DOI: 10.1021/ar500375j. View

20.

Gandeepan P, Muller T, Zell D, Cera G, Warratz S, Ackermann L . 3d Transition Metals for C-H Activation. Chem Rev. 2018; 119(4):2192-2452. DOI: 10.1021/acs.chemrev.8b00507. View