Synthesis of β-Diamine Building Blocks by Photocatalytic Hydroamination of Enecarbamates with Amines, Ammonia and N-H Heterocycles

Overview

Journal Chemistry

Specialty Chemistry

Date 2020 Aug 28

PMID 32853417

Citations 3

Authors

Daniel Francis

Adam Nelson

Stephen P Marsden

Affiliations

Soon will be listed here.

Abstract

3-Amino-substituted saturated nitrogen heterocycles are an important subclass of β-diamines, appearing in a number of clinical agents. Herein, we report a unified approach to these products based upon the regioselective photoredox-mediated hydroamination of enecarbamates. The amine coupling partner can encompass diverse amine types under a single set of reaction conditions, including primary alkyl amines, ammonia, aryl and heteroaryl amines, and N-H heterocycles. The method enables the synthesis of a wide range of pharmaceutically relevant building blocks.

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Synthesis of β-Diamine Building Blocks by Photocatalytic Hydroamination of Enecarbamates with Amines, Ammonia and N-H Heterocycles.

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References

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

Kemper J, Studer A . Stable reagents for the generation of N-centered radicals: hydroamination of norbornene. Angew Chem Int Ed Engl. 2005; 44(31):4914-7. DOI: 10.1002/anie.200463032. View

Gunthorpe M, Hannan S, Smart D, Jerman J, Arpino S, Smith G . Characterization of SB-705498, a potent and selective vanilloid receptor-1 (VR1/TRPV1) antagonist that inhibits the capsaicin-, acid-, and heat-mediated activation of the receptor. J Pharmacol Exp Ther. 2007; 321(3):1183-92. DOI: 10.1124/jpet.106.116657. View

Guin J, Muck-Lichtenfeld C, Grimme S, Studer A . Radical transfer hydroamination with aminated cyclohexadienes using polarity reversal catalysis: scope and limitations. J Am Chem Soc. 2007; 129(14):4498-503. DOI: 10.1021/ja0692581. View

Margrey K, Nicewicz D . A General Approach to Catalytic Alkene Anti-Markovnikov Hydrofunctionalization Reactions via Acridinium Photoredox Catalysis. Acc Chem Res. 2016; 49(9):1997-2006. DOI: 10.1021/acs.accounts.6b00304. View

Roos C, Demaerel J, Graff D, Knowles R . Enantioselective Hydroamination of Alkenes with Sulfonamides Enabled by Proton-Coupled Electron Transfer. J Am Chem Soc. 2020; 142(13):5974-5979. PMC: 7468321. DOI: 10.1021/jacs.0c01332. View

Lucet D, Le Gall T, Mioskowski C . The Chemistry of Vicinal Diamines. Angew Chem Int Ed Engl. 2018; 37(19):2580-2627. DOI: 10.1002/(SICI)1521-3773(19981016)37:19<2580::AID-ANIE2580>3.0.CO;2-L. View

Nguyen S, Zhu Q, Knowles R . PCET-Enabled Olefin Hydroamidation Reactions with -Alkyl Amides. ACS Catal. 2020; 9(5):4502-4507. PMC: 7156045. DOI: 10.1021/acscatal.9b00966. View

Adouama C, Keyrouz R, Pilet G, Monnereau C, Gueyrard D, Noel T . Access to cyclic gem-difluoroacyl scaffolds via electrochemical and visible light photocatalytic radical tandem cyclization of heteroaryl chlorodifluoromethyl ketones. Chem Commun (Camb). 2017; 53(41):5653-5656. DOI: 10.1039/c7cc02979a. View

10.

Zhang J, Ward K . Besifloxacin, a novel fluoroquinolone antimicrobial agent, exhibits potent inhibition of pro-inflammatory cytokines in human THP-1 monocytes. J Antimicrob Chemother. 2007; 61(1):111-6. DOI: 10.1093/jac/dkm398. View

11.

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

12.

Pan Z, Scheerens H, Li S, Schultz B, Sprengeler P, Burrill L . Discovery of selective irreversible inhibitors for Bruton's tyrosine kinase. ChemMedChem. 2006; 2(1):58-61. DOI: 10.1002/cmdc.200600221. View

13.

Musacchio A, Nguyen L, Beard G, Knowles R . Catalytic olefin hydroamination with aminium radical cations: a photoredox method for direct C-N bond formation. J Am Chem Soc. 2014; 136(35):12217-20. DOI: 10.1021/ja5056774. View

14.

Musacchio A, Lainhart B, Zhang X, Naguib S, Sherwood T, Knowles R . Catalytic intermolecular hydroaminations of unactivated olefins with secondary alkyl amines. Science. 2017; 355(6326):727-730. PMC: 5426363. DOI: 10.1126/science.aal3010. View

15.

Zhu Q, Graff D, Knowles R . Intermolecular Anti-Markovnikov Hydroamination of Unactivated Alkenes with Sulfonamides Enabled by Proton-Coupled Electron Transfer. J Am Chem Soc. 2017; 140(2):741-747. PMC: 6247111. DOI: 10.1021/jacs.7b11144. View

16.

Trindade A, Faulkner E, Leach A, Nelson A, Marsden S . Fragment-oriented synthesis: β-elaboration of cyclic amine fragments using enecarbamates as platform intermediates. Chem Commun (Camb). 2020; 56(62):8802-8805. DOI: 10.1039/d0cc03934a. View

17.

Miller D, Ganley J, Musacchio A, Sherwood T, Ewing W, Knowles R . Anti-Markovnikov Hydroamination of Unactivated Alkenes with Primary Alkyl Amines. J Am Chem Soc. 2019; 141(42):16590-16594. PMC: 7202396. DOI: 10.1021/jacs.9b08746. View

18.

Murray C, Rees D . Opportunity Knocks: Organic Chemistry for Fragment-Based Drug Discovery (FBDD). Angew Chem Int Ed Engl. 2015; 55(2):488-92. DOI: 10.1002/anie.201506783. View

19.

Changelian P, Flanagan M, Ball D, Kent C, Magnuson K, Martin W . Prevention of organ allograft rejection by a specific Janus kinase 3 inhibitor. Science. 2003; 302(5646):875-8. DOI: 10.1126/science.1087061. View

20.

Klinkenberg J, Hartwig J . Catalytic organometallic reactions of ammonia. Angew Chem Int Ed Engl. 2010; 50(1):86-95. PMC: 3261073. DOI: 10.1002/anie.201002354. View