Pd(ii)-catalyzed Remote Regiodivergent - and -C-H Functionalizations of Phenylethylamines

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2018 Jun 5

PMID 29861897

Citations 17

Authors

Shangda Li

Huafang Ji

Lei Cai

Gang Li

Affiliations

Soon will be listed here.

Abstract

Site selectivity control is of vital importance in the direct functionalization of inert C-H bonds. Reported here is a novel example of remote regiodivergent - and -C-H bond functionalizations of phenylethylamine derivatives by using a novel 2-cyanobenzoyl group as the original directing functionality, where the regioselectivity was adjusted by a methylation. The potential of the method was exemplified by sequential functionalizations of both - and -C-H bonds of a phenylethylamine derivative in a streamlined manner.

Citing Articles

Pd(ii)-catalyzed -C-H bromination and chlorination of aniline and benzoic acid derivatives.

Wang H, Fu L, Zhou C, Li G Chem Sci. 2022; 13(29):8686-8692.

PMID: 35974770 PMC: 9337732. DOI: 10.1039/d2sc01834a.

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.

Empirical Guidelines for the Development of Remote Directing Templates through Quantitative and Experimental Analyses.

Lam N, Fan Z, Wu K, Park H, Shim S, Strassfeld D J Am Chem Soc. 2022; 144(6):2793-2803.

PMID: 35108009 PMC: 9170077. DOI: 10.1021/jacs.1c12654.

Recent development in transition metal-catalysed C-H olefination.

Ali W, Prakash G, Maiti D Chem Sci. 2021; 12(8):2735-2759.

PMID: 34164039 PMC: 8179420. DOI: 10.1039/d0sc05555g.

Nickel-catalyzed C-O/N-H, C-S/N-H, and C-CN/N-H annulation of aromatic amides with alkynes: C-O, C-S, and C-CN activation.

Iyori Y, Ueno R, Morishige A, Chatani N Chem Sci. 2021; 12(5):1772-1777.

PMID: 34163938 PMC: 8179272. DOI: 10.1039/d0sc06056a.

References

Arockiam P, Bruneau C, Dixneuf P . Ruthenium(II)-catalyzed C-H bond activation and functionalization. Chem Rev. 2012; 112(11):5879-918. DOI: 10.1021/cr300153j. View

Li J, Mei T, Yu J . Synthesis of indolines and tetrahydroisoquinolines from arylethylamines by Pd(II)-catalyzed C-H activation reactions. Angew Chem Int Ed Engl. 2008; 47(34):6452-5. DOI: 10.1002/anie.200802187. View

Saget T, Cramer N . Enantioselective C-H arylation strategy for functionalized dibenzazepinones with quaternary stereocenters. Angew Chem Int Ed Engl. 2013; 52(30):7865-8. DOI: 10.1002/anie.201303816. View

Shrestha R, Mukherjee P, Tan Y, Litman Z, Hartwig J . Sterically controlled, palladium-catalyzed intermolecular amination of arenes. J Am Chem Soc. 2013; 135(23):8480-3. DOI: 10.1021/ja4032677. View

Cornella J, Righi M, Larrosa I . Carboxylic acids as traceless directing groups for formal meta-selective direct arylation. Angew Chem Int Ed Engl. 2011; 50(40):9429-32. DOI: 10.1002/anie.201103720. View

Yamaguchi J, Yamaguchi A, Itami K . C-H bond functionalization: emerging synthetic tools for natural products and pharmaceuticals. Angew Chem Int Ed Engl. 2012; 51(36):8960-9009. DOI: 10.1002/anie.201201666. View

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

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

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

10.

Kwak J, Kim M, Chang S . Rh(NHC)-catalyzed direct and selective arylation of quinolines at the 8-position. J Am Chem Soc. 2011; 133(11):3780-3. DOI: 10.1021/ja111670s. View

11.

Cheng C, Hartwig J . Rhodium-catalyzed intermolecular C-H silylation of arenes with high steric regiocontrol. Science. 2014; 343(6173):853-7. DOI: 10.1126/science.1248042. View

12.

Dick A, Hull K, Sanford M . A highly selective catalytic method for the oxidative functionalization of C-H bonds. J Am Chem Soc. 2004; 126(8):2300-1. DOI: 10.1021/ja031543m. View

13.

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

14.

Saidi O, Marafie J, Ledger A, Liu P, Mahon M, Kociok-Kohn G . Ruthenium-catalyzed meta sulfonation of 2-phenylpyridines. J Am Chem Soc. 2011; 133(48):19298-301. DOI: 10.1021/ja208286b. View

15.

Cho S, Kim J, Kwak J, Chang S . Recent advances in the transition metal-catalyzed twofold oxidative C-H bond activation strategy for C-C and C-N bond formation. Chem Soc Rev. 2011; 40(10):5068-83. DOI: 10.1039/c1cs15082k. View

16.

Cho J, Tse M, Holmes D, Maleczka Jr R, Smith 3rd M . Remarkably selective iridium catalysts for the elaboration of aromatic C-H bonds. Science. 2001; 295(5553):305-8. DOI: 10.1126/science.1067074. View

17.

Campbell A, Meyer E, Stahl S . Regiocontrolled aerobic oxidative coupling of indoles and benzene using Pd catalysts with 4,5-diazafluorene ligands. Chem Commun (Camb). 2011; 47(37):10257-9. PMC: 3228523. DOI: 10.1039/c1cc13632a. View

18.

Gutekunst W, Baran P . Total synthesis and structural revision of the piperarborenines via sequential cyclobutane C-H arylation. J Am Chem Soc. 2011; 133(47):19076-9. PMC: 3223735. DOI: 10.1021/ja209205x. View

19.

Chen D, Youn S . C-H activation: a complementary tool in the total synthesis of complex natural products. Chemistry. 2012; 18(31):9452-74. DOI: 10.1002/chem.201201329. View

20.

Lafrance M, Gorelsky S, Fagnou K . High-yielding palladium-catalyzed intramolecular alkane arylation: reaction development and mechanistic studies. J Am Chem Soc. 2007; 129(47):14570-1. DOI: 10.1021/ja076588s. View