Ligand Controlled Ir-Catalyzed Regiodivergent Oxyamination of Unactivated Alkenes

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2019 Jul 17

PMID 31310537

Citations 7

Authors

Honghui Lei

John H Conway Jr

Caleb C Cook

Tomislav Rovis

Affiliations

Soon will be listed here.

Abstract

An intramolecular Ir(III)-catalyzed regiodivergent oxyamination of unactivated alkenes provides valuable γ-lactams, γ-lactones and δ-lactams. The regioselectivity is controlled by the electronically tunable cyclopentadienyl Ir(III)-complexes enabling oxyamination via either 5-exo or 6-endo pathways. With respect to the mechanism, we propose a highly reactive [3.1.0] bicycle intermediate derived from Ir(V) nitrene-mediated aziridination to be a key intermediate toward the synthesis of γ-lactams.

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References

Cho I, Prier C, Jia Z, Zhang R, Gorbe T, Arnold F . Enantioselective Aminohydroxylation of Styrenyl Olefins Catalyzed by an Engineered Hemoprotein. Angew Chem Int Ed Engl. 2019; 58(10):3138-3142. DOI: 10.1002/anie.201812968. View

Hong S, Chang S . Stereodefined Access to Lactams via Olefin Difunctionalization: Iridium Nitrenoids as a Motif of LUMO-Controlled Dipoles. J Am Chem Soc. 2019; 141(26):10399-10408. DOI: 10.1021/jacs.9b04317. View

Williamson K, Yoon T . Iron-catalyzed aminohydroxylation of olefins. J Am Chem Soc. 2010; 132(13):4570-1. PMC: 2857537. DOI: 10.1021/ja1013536. View

Zhu R, Buchwald S . Versatile Enantioselective Synthesis of Functionalized Lactones via Copper-Catalyzed Radical Oxyfunctionalization of Alkenes. J Am Chem Soc. 2015; 137(25):8069-77. PMC: 4490856. DOI: 10.1021/jacs.5b04821. View

Conway Jr J, Rovis T . Regiodivergent Iridium(III)-Catalyzed Diamination of Alkenyl Amides with Secondary Amines: Complementary Access to γ- or δ-Lactams. J Am Chem Soc. 2017; 140(1):135-138. PMC: 5973537. DOI: 10.1021/jacs.7b11455. View

de Haro T, Nevado C . Flexible gold-catalyzed regioselective oxidative difunctionalization of unactivated alkenes. Angew Chem Int Ed Engl. 2011; 50(4):906-10. DOI: 10.1002/anie.201005763. View

Williamson K, Yoon T . Iron catalyzed asymmetric oxyamination of olefins. J Am Chem Soc. 2012; 134(30):12370-3. PMC: 3422551. DOI: 10.1021/ja3046684. View

Donohoe T, Callens C, Flores A, Lacy A, Rathi A . Recent developments in methodology for the direct oxyamination of olefins. Chemistry. 2011; 17(1):58-76. DOI: 10.1002/chem.201002323. View

Zhang B, Studer A . Stereoselective radical azidooxygenation of alkenes. Org Lett. 2013; 15(17):4548-51. DOI: 10.1021/ol402106x. View

10.

Lorpitthaya R, Xie Z, Kuo J, Liu X . Stereocontrolled intramolecular aziridination of glycals: ready access to aminoglycosides and mechanistic insights from DFT studies. Chemistry. 2007; 14(5):1561-70. DOI: 10.1002/chem.200701288. View

11.

Chemler S, Karyakarte S, Khoder Z . Stereoselective and Regioselective Synthesis of Heterocycles via Copper-Catalyzed Additions of Amine Derivatives and Alcohols to Alkenes. J Org Chem. 2017; 82(21):11311-11325. PMC: 5782808. DOI: 10.1021/acs.joc.7b02072. View

12.

OBrien P . Sharpless Asymmetric Aminohydroxylation: Scope, Limitations, and Use in Synthesis. Angew Chem Int Ed Engl. 2018; 38(3):326-329. DOI: 10.1002/(SICI)1521-3773(19990201)38:3<326::AID-ANIE326>3.0.CO;2-T. View

13.

Levites-Agababa E, Menhaji E, Perlson L, Rojas C . Amidoglycosylation via metal-catalyzed internal nitrogen atom delivery. Org Lett. 2002; 4(5):863-5. DOI: 10.1021/ol025634k. View

14.

Morgan A, Masse C, Panek J . Reversal of regioselection in the sharpless asymmetric aminohydroxylation of aryl ester substrates. Org Lett. 2000; 1(12):1949-52. DOI: 10.1021/ol9903032. View

15.

Zhu H, Chen P, Liu G . Pd-catalyzed intramolecular aminohydroxylation of alkenes with hydrogen peroxide as oxidant and water as nucleophile. J Am Chem Soc. 2014; 136(5):1766-9. DOI: 10.1021/ja412023b. View

16.

Romanov-Michailidis F, Ravetz B, Paley D, Rovis T . Ir(III)-Catalyzed Carbocarbation of Alkynes through Undirected Double C-H Bond Activation of Anisoles. J Am Chem Soc. 2018; 140(16):5370-5374. PMC: 5972829. DOI: 10.1021/jacs.8b02716. View

17.

Padwa A, Stengel T . Stereochemical aspects of the iodine(III)-mediated aziridination reaction of some cyclic allylic carbamates. Org Lett. 2002; 4(13):2137-9. DOI: 10.1021/ol0259490. View

18.

Jiang H, Lang K, Lu H, Wojtas L, Zhang X . Asymmetric Radical Bicyclization of Allyl Azidoformates via Cobalt(II)-Based Metalloradical Catalysis. J Am Chem Soc. 2017; 139(27):9164-9167. PMC: 5553632. DOI: 10.1021/jacs.7b05778. View

19.

Gigant N, Dequirez G, Retailleau P, Gillaizeau I, Dauban P . Catalytic selective oxyamidation of cyclic enamides using nitrenes. Chemistry. 2011; 18(1):90-4. DOI: 10.1002/chem.201102302. View

20.

Dequirez G, Ciesielski J, Retailleau P, Dauban P . Catalytic intermolecular alkene oxyamination with nitrenes. Chemistry. 2014; 20(29):8929-33. DOI: 10.1002/chem.201400301. View