Catalytic β C-H Amination an Imidate Radical Relay

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2019 Apr 19

PMID 30996986

Citations 18

Authors

Leah M Stateman

Ethan A Wappes

Kohki M Nakafuku

Kara M Edwards

David A Nagib

Affiliations

Soon will be listed here.

Abstract

The first catalytic strategy to harness imidate radicals for C-H functionalization has been developed. This iodine-catalyzed approach enables β C-H amination of alcohols by an imidate-mediated radical relay. In contrast to our first-generation, (super)stoichiometric protocol, this catalytic method enables faster and more efficient reactivity. Furthermore, lower oxidant concentration affords broader functional group tolerance, including alkenes, alkynes, alcohols, carbonyls, and heteroarenes. Mechanistic experiments interrogating the electronic nature of the key 1,5 H-atom transfer event are included, as well as probes for chemo-, regio-, and stereo-selectivity.

Citing Articles

Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents.

Yoshimura A, Zhdankin V Chem Rev. 2024; 124(19):11108-11186.

PMID: 39269928 PMC: 11468727. DOI: 10.1021/acs.chemrev.4c00303.

Strategies for Accessing -1-Amino-2-Indanol.

Mendas I, Gastaldi S, Suppo J Molecules. 2024; 29(11).

PMID: 38893318 PMC: 11173559. DOI: 10.3390/molecules29112442.

Recent advances in visible light-induced C( )-N bond formation.

Rivas M, Palchykov V, Jia X, Gevorgyan V Nat Rev Chem. 2023; 6(8):544-561.

PMID: 37034136 PMC: 10074542. DOI: 10.1038/s41570-022-00403-8.

γ C-H Functionalization of Amines via Triple H-Atom Transfer of a Vinyl Sulfonyl Radical Chaperone.

Herbort J, Bednar T, Chen A, RajanBabu T, Nagib D J Am Chem Soc. 2022; 144(29):13366-13373.

PMID: 35820104 PMC: 9405708. DOI: 10.1021/jacs.2c05266.

δ-C-H Halogenation Reactions Enabled by a Nitrogen-Centered Radical Precursor.

Herron A, Hsu C, Yu J Org Lett. 2022; 24(20):3652-3656.

PMID: 35549294 PMC: 10292861. DOI: 10.1021/acs.orglett.2c01261.

References

Ager D, Prakash I, Schaad D . 1,2-Amino Alcohols and Their Heterocyclic Derivatives as Chiral Auxiliaries in Asymmetric Synthesis. Chem Rev. 1996; 96(2):835-876. DOI: 10.1021/cr9500038. View

Francisco C, Herrera A, Suarez E . Intramolecular hydrogen abstraction reaction promoted by N-radicals in carbohydrates. Synthesis of chiral 7-oxa-2-azabicyclo[2.2.1]heptane and 8-oxa-6-azabicyclo[3.2.1]octane ring systems. J Org Chem. 2003; 68(3):1012-7. DOI: 10.1021/jo026314h. View

Cui Y, He C . A silver-catalyzed intramolecular amidation of saturated C--h bonds. Angew Chem Int Ed Engl. 2004; 43(32):4210-2. DOI: 10.1002/anie.200454243. View

Lebel H, Huard K, Lectard S . N-tosyloxycarbamates as a source of metal nitrenes: rhodium-catalyzed C-H insertion and aziridination reactions. J Am Chem Soc. 2005; 127(41):14198-9. DOI: 10.1021/ja0552850. View

Nam P, Nguyen M, Chandra A . The C-H and alpha(C-X) bond dissociation enthalpies of toluene, C6H5-CH2X (X = F, Cl), and their substituted derivatives: a DFT study. J Phys Chem A. 2006; 109(45):10342-7. DOI: 10.1021/jp0534030. View

Fraunhoffer K, White M . syn-1,2-Amino alcohols via diastereoselective allylic C-H amination. J Am Chem Soc. 2007; 129(23):7274-6. PMC: 2720786. DOI: 10.1021/ja071905g. View

Davies H, Manning J . Catalytic C-H functionalization by metal carbenoid and nitrenoid insertion. Nature. 2008; 451(7177):417-24. PMC: 3033428. DOI: 10.1038/nature06485. View

Chen K, Richter J, Baran P . 1,3-Diol synthesis via controlled, radical-mediated C-H functionalization. J Am Chem Soc. 2008; 130(23):7247-9. DOI: 10.1021/ja802491q. View

Zard S . Recent progress in the generation and use of nitrogen-centred radicals. Chem Soc Rev. 2008; 37(8):1603-18. DOI: 10.1039/b613443m. View

10.

Coniglio A, Galli C, Gentili P, Vadala R . Hydrogen atom abstraction from C-H bonds of benzylamides by the aminoxyl radical BTNO: a kinetic study. Org Biomol Chem. 2008; 7(1):155-60. DOI: 10.1039/b815584d. View

11.

Uyanik M, Okamoto H, Yasui T, Ishihara K . Quaternary ammonium (hypo)iodite catalysis for enantioselective oxidative cycloetherification. Science. 2010; 328(5984):1376-9. DOI: 10.1126/science.1188217. View

12.

Koag M, Lee S . Discovery of hypoiodite-mediated aminyl radical cyclization lacking a nitrogen radical-stabilizing group: application to synthesis of an oxazaspiroketal-containing cephalostatin analog. Org Lett. 2011; 13(18):4766-9. DOI: 10.1021/ol2017033. View

13.

Simmons E, Hartwig J . Catalytic functionalization of unactivated primary C-H bonds directed by an alcohol. Nature. 2012; 483(7387):70-3. PMC: 11620535. DOI: 10.1038/nature10785. View

14.

Karjalainen O, Koskinen A . Diastereoselective synthesis of vicinal amino alcohols. Org Biomol Chem. 2012; 10(22):4311-26. DOI: 10.1039/c2ob25357g. View

15.

Roizen J, Harvey M, Du Bois J . Metal-catalyzed nitrogen-atom transfer methods for the oxidation of aliphatic C-H bonds. Acc Chem Res. 2012; 45(6):911-22. PMC: 5483381. DOI: 10.1021/ar200318q. View

16.

Ren Z, Mo F, Dong G . Catalytic functionalization of unactivated sp3 C-H bonds via exo-directing groups: synthesis of chemically differentiated 1,2-diols. J Am Chem Soc. 2012; 134(41):16991-4. DOI: 10.1021/ja3082186. View

17.

Hennessy E, Betley T . Complex N-heterocycle synthesis via iron-catalyzed, direct C-H bond amination. Science. 2013; 340(6132):591-5. DOI: 10.1126/science.1233701. View

18.

Collins K, Glorius F . A robustness screen for the rapid assessment of chemical reactions. Nat Chem. 2013; 5(7):597-601. DOI: 10.1038/nchem.1669. View

19.

He G, Zhang S, Nack W, Li Q, Chen G . Use of a readily removable auxiliary group for the synthesis of pyrrolidones by the palladium-catalyzed intramolecular amination of unactivated γ C(sp(3))-H bonds. Angew Chem Int Ed Engl. 2013; 52(42):11124-8. DOI: 10.1002/anie.201305615. View

20.

Wang Z, Ni J, Kuninobu Y, Kanai M . Copper-catalyzed intramolecular C(sp³)-H and C(sp²)-H amidation by oxidative cyclization. Angew Chem Int Ed Engl. 2014; 53(13):3496-9. DOI: 10.1002/anie.201311105. View