PCET-Enabled Olefin Hydroamidation Reactions with -Alkyl Amides

Overview

Journal ACS Catal

Publisher American Chemical Society

Date 2020 Apr 16

PMID 32292642

Citations 19

Authors

Suong T Nguyen

Qilei Zhu

Robert R Knowles

Affiliations

Soon will be listed here.

Abstract

Olefin aminations are important synthetic technologies for the construction of aliphatic C-N bonds. Here we report a catalytic protocol for olefin hydroamidation that proceeds through transient amidyl radical intermediates that are formed via proton-coupled electron transfer (PCET) activation of the strong N-H bonds in -alkyl amides by an excited-state iridium photocatalyst and a dialkyl phosphate base. This method exhibits a broad substrate scope, high functional group tolerance, and amenability to use in cascade polycyclization reactions. The feasibility of this PCET protocol in enabling the intermolecular anti-Markovnikov hydroamidation reactions of unactivated olefins is also demonstrated.

Citing Articles

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References

Yuan X, Liu K, Li C . Development of highly regioselective amidyl radical cyclization based on lone pair-lone pair repulsion. J Org Chem. 2008; 73(16):6166-71. DOI: 10.1021/jo800845b. View

Williamson J, Czaplyski W, Alexanian E, Leibfarth F . Regioselective C-H Xanthylation as a Platform for Polyolefin Functionalization. Angew Chem Int Ed Engl. 2018; 57(21):6261-6265. DOI: 10.1002/anie.201803020. View

Lalonde R, Brenzovich Jr W, Benitez D, Tkatchouk E, Kelley K, Goddard 3rd W . Alkylgold complexes by the intramolecular aminoauration of unactivated alkenes. Chem Sci. 2013; 1(2). PMC: 3866133. DOI: 10.1039/C0SC00255K. View

Zhang S, Li L, Xue M, Zhang R, Xu K, Zeng C . Electrochemical Formation of N-Acyloxy Amidyl Radicals and Their Application: Regioselective Intramolecular Amination of sp and sp C-H Bonds. Org Lett. 2018; 20(12):3443-3446. DOI: 10.1021/acs.orglett.8b00981. View

Chu J, Rovis T . Amide-directed photoredox-catalysed C-C bond formation at unactivated sp C-H bonds. Nature. 2016; 539(7628):272-275. PMC: 5574171. DOI: 10.1038/nature19810. View

Hu X, Qi X, Chen J, Zhao Q, Wei Q, Lan Y . Catalytic N-radical cascade reaction of hydrazones by oxidative deprotonation electron transfer and TEMPO mediation. Nat Commun. 2016; 7:11188. PMC: 4823831. DOI: 10.1038/ncomms11188. View

Wu F, Wang L, Chen J, Nicewicz D, Huang Y . Direct Synthesis of Polysubstituted Aldehydes via Visible-Light Catalysis. Angew Chem Int Ed Engl. 2018; 57(8):2174-2178. DOI: 10.1002/anie.201712384. View

Rucker R, Whittaker A, Dang H, Lalic G . Synthesis of tertiary alkyl amines from terminal alkenes: copper-catalyzed amination of alkyl boranes. J Am Chem Soc. 2012; 134(15):6571-4. DOI: 10.1021/ja3023829. View

Zhang Z, Lee S, Widenhoefer R . Intermolecular hydroamination of ethylene and 1-alkenes with cyclic ureas catalyzed by achiral and chiral gold(I) complexes. J Am Chem Soc. 2009; 131(15):5372-3. PMC: 2891684. DOI: 10.1021/ja9001162. View

10.

Miller D, Choi G, Orbe H, Knowles R . Catalytic Olefin Hydroamidation Enabled by Proton-Coupled Electron Transfer. J Am Chem Soc. 2015; 137(42):13492-5. PMC: 4629195. DOI: 10.1021/jacs.5b09671. View

11.

Janza B, Studer A . Stereoselective cyclization reactions of IBX-generated alkoxyamidyl radicals. J Org Chem. 2005; 70(17):6991-4. DOI: 10.1021/jo0509399. View

12.

Schmidt V, Quinn R, Brusoe A, Alexanian E . Site-selective aliphatic C-H bromination using N-bromoamides and visible light. J Am Chem Soc. 2014; 136(41):14389-92. DOI: 10.1021/ja508469u. View

13.

Lardy S, Schmidt V . Intermolecular Radical Mediated Anti-Markovnikov Alkene Hydroamination Using N-Hydroxyphthalimide. J Am Chem Soc. 2018; 140(39):12318-12322. DOI: 10.1021/jacs.8b06881. View

14.

Komeyama K, Morimoto T, Takaki K . A simple and efficient iron-catalyzed intramolecular hydroamination of unactivated olefins. Angew Chem Int Ed Engl. 2006; 45(18):2938-41. DOI: 10.1002/anie.200503789. View

15.

Zheng S, Gutierrez-Bonet A, Molander G . Merging Photoredox PCET with Nickel-Catalyzed Cross-Coupling: Cascade Amidoarylation of Unactivated Olefins. Chem. 2019; 5(2):339-352. PMC: 6508594. DOI: 10.1016/j.chempr.2018.11.014. View

16.

Goossen L, Salih K, Blanchot M . Synthesis of secondary enamides by ruthenium-catalyzed selective addition of amides to terminal alkynes. Angew Chem Int Ed Engl. 2008; 47(44):8492-5. DOI: 10.1002/anie.200803068. View

17.

Zhu S, Buchwald S . Enantioselective CuH-catalyzed anti-Markovnikov hydroamination of 1,1-disubstituted alkenes. J Am Chem Soc. 2014; 136(45):15913-6. PMC: 4235366. DOI: 10.1021/ja509786v. View

18.

Ensign S, Vanable E, Kortman G, Weir L, Hull K . Anti-Markovnikov Hydroamination of Homoallylic Amines. J Am Chem Soc. 2015; 137(43):13748-51. DOI: 10.1021/jacs.5b08500. View

19.

Carestia A, Ravelli D, Alexanian E . Reagent-dictated site selectivity in intermolecular aliphatic C-H functionalizations using nitrogen-centered radicals. Chem Sci. 2018; 9(24):5360-5365. PMC: 6009468. DOI: 10.1039/c8sc01756e. View

20.

Nicolaou K, Baran P, Barluenga S, Hunt K, Kranich R, Vega J . Iodine(V) reagents in organic synthesis. Part 3. New routes to heterocyclic compounds via o-iodoxybenzoic acid-mediated cyclizations: generality, scope, and mechanism. J Am Chem Soc. 2002; 124(10):2233-44. DOI: 10.1021/ja012126h. View