Rhodium Catalyzed Template-assisted Distal -C-H Olefination

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2019 Sep 7

PMID 31489165

Citations 15

Authors

Uttam Dutta

Sudip Maiti

Sandeep Pimparkar

Siddhartha Maiti

Lawrence R Gahan

Elizabeth H Krenske

David W Lupton

Debabrata Maiti

Affiliations

Soon will be listed here.

Abstract

Rhodium catalysis has been extensively used for -C-H functionalization reactions, and successfully extended to -C-H functionalization. Its application to -C-H activation remains an unmet challenge. Herein we disclose the first example of such a reaction, with the Rh-catalyzed -C-H olefination of arenes. The use of a Si-linked cyanobiphenyl unit as a traceless directing group leads to highly -selective arene-olefin couplings.

Citing Articles

Directing group assisted -selective C-H alkynylation of unbiased arenes enabled by rhodium catalysis.

Dutta U, Prakash G, Devi K, Borah K, Zhang X, Maiti D Chem Sci. 2023; 14(41):11381-11388.

PMID: 37886091 PMC: 10599460. DOI: 10.1039/d3sc03528j.

Remote C-H Olefination of Heterocyclic Biaryls Enabled by Reversibly Bound Templates.

Liu L, Fan Z, Hoque M, Qian S, Meng G, Chekshin N Angew Chem Int Ed Engl. 2023; 62(37):e202307581.

PMID: 37470111 PMC: 10552871. DOI: 10.1002/anie.202307581.

Transition-Metal-Catalyzed C-H Bond Activation for the Formation of C-C Bonds in Complex Molecules.

Docherty J, Lister T, McArthur G, Findlay M, Domingo-Legarda P, Kenyon J Chem Rev. 2023; 123(12):7692-7760.

PMID: 37163671 PMC: 10311463. DOI: 10.1021/acs.chemrev.2c00888.

Expanding chemical space by para-C-H arylation of arenes.

Maiti S, Li Y, Sasmal S, Guin S, Bhattacharya T, Lahiri G Nat Commun. 2022; 13(1):3963.

PMID: 35803905 PMC: 9270437. DOI: 10.1038/s41467-022-31506-x.

Directing group assisted rhodium catalyzed -C-H alkynylation of arenes.

Sasmal S, Prakash G, Dutta U, Laskar R, Lahiri G, Maiti D Chem Sci. 2022; 13(19):5616-5621.

PMID: 35694332 PMC: 9116288. DOI: 10.1039/d2sc00982j.

References

Topczewski J, Sanford M . Carbon-Hydrogen (C-H) Bond Activation at Pd: A Frontier in C-H Functionalization Catalysis. Chem Sci. 2014; 6(1):70-76. PMC: 4275847. DOI: 10.1039/C4SC02591A. View

Hofmann N, Ackermann L . meta-Selective C-H bond alkylation with secondary alkyl halides. J Am Chem Soc. 2013; 135(15):5877-84. DOI: 10.1021/ja401466y. View

Okumura S, Nakao Y . para-Selective Alkylation of Sulfonylarenes by Cooperative Nickel/Aluminum Catalysis. Org Lett. 2017; 19(3):584-587. DOI: 10.1021/acs.orglett.6b03741. View

Wang X, Gong W, Fang L, Zhu R, Li S, Engle K . Ligand-enabled meta-C-H activation using a transient mediator. Nature. 2015; 519(7543):334-8. PMC: 4368492. DOI: 10.1038/nature14214. View

Bera M, Maji A, Sahoo S, Maiti D . Palladium(II)-Catalyzed meta-C-H Olefination: Constructing Multisubstituted Arenes through Homo-Diolefination and Sequential Hetero-Diolefination. Angew Chem Int Ed Engl. 2015; 54(29):8515-9. DOI: 10.1002/anie.201503112. View

Yang L, Semba K, Nakao Y . para-Selective C-H Borylation of (Hetero)Arenes by Cooperative Iridium/Aluminum Catalysis. Angew Chem Int Ed Engl. 2017; 56(17):4853-4857. DOI: 10.1002/anie.201701238. View

Phipps R, Gaunt M . A meta-selective copper-catalyzed C-H bond arylation. Science. 2009; 323(5921):1593-7. DOI: 10.1126/science.1169975. View

Park S, Kim J, Chang S . Rhodium-catalyzed selective olefination of arene esters via C-H bond activation. Org Lett. 2011; 13(9):2372-5. DOI: 10.1021/ol200600p. View

Colby D, Tsai A, Bergman R, Ellman J . Rhodium catalyzed chelation-assisted C-H bond functionalization reactions. Acc Chem Res. 2011; 45(6):814-25. PMC: 3307943. DOI: 10.1021/ar200190g. View

10.

Jin Z, Chu L, Chen Y, Yu J . Pd-Catalyzed Remote Meta-C-H Functionalization of Phenylacetic Acids Using a Pyridine Template. Org Lett. 2018; 20(2):425-428. DOI: 10.1021/acs.orglett.7b03336. View

11.

Colby D, Bergman R, Ellman J . Rhodium-catalyzed C-C bond formation via heteroatom-directed C-H bond activation. Chem Rev. 2009; 110(2):624-55. PMC: 2820156. DOI: 10.1021/cr900005n. View

12.

Maji A, Dahiya A, Lu G, Bhattacharya T, Brochetta M, Zanoni G . H-bonded reusable template assisted para-selective ketonisation using soft electrophilic vinyl ethers. Nat Commun. 2018; 9(1):3582. PMC: 6123475. DOI: 10.1038/s41467-018-06018-2. View

13.

Robbins D, Hartwig J . Sterically controlled alkylation of arenes through iridium-catalyzed C-H borylation. Angew Chem Int Ed Engl. 2012; 52(3):933-7. DOI: 10.1002/anie.201208203. View

14.

Daugulis O, Do H, Shabashov D . Palladium- and copper-catalyzed arylation of carbon-hydrogen bonds. Acc Chem Res. 2009; 42(8):1074-86. PMC: 2846291. DOI: 10.1021/ar9000058. View

15.

Xu H, Kang Y, Shi H, Zhang P, Chen Y, Zhang B . Rh(III)-Catalyzed meta-C-H Alkenylation with Alkynes. J Am Chem Soc. 2018; 141(1):76-79. DOI: 10.1021/jacs.8b11038. View

16.

Drapeau M, Goossen L . Carboxylic Acids as Directing Groups for C-H Bond Functionalization. Chemistry. 2016; 22(52):18654-18677. DOI: 10.1002/chem.201603263. View

17.

Leow D, Li G, Mei T, Yu J . Activation of remote meta-C-H bonds assisted by an end-on template. Nature. 2012; 486(7404):518-22. PMC: 3386562. DOI: 10.1038/nature11158. View

18.

Bag S, Patra T, Modak A, Deb A, Maity S, Dutta U . Remote para-C-H Functionalization of Arenes by a D-Shaped Biphenyl Template-Based Assembly. J Am Chem Soc. 2015; 137(37):11888-91. DOI: 10.1021/jacs.5b06793. View

19.

Patureau F, Glorius F . Rh catalyzed olefination and vinylation of unactivated acetanilides. J Am Chem Soc. 2010; 132(29):9982-3. DOI: 10.1021/ja103834b. View

20.

Sun C, Li B, Shi Z . Direct C-H transformation via iron catalysis. Chem Rev. 2010; 111(3):1293-314. DOI: 10.1021/cr100198w. View