Examination of the Mechanism of Rh(2)(II)-catalyzed Carbazole Formation Using Intramolecular Competition Experiments

Overview

Journal J Org Chem

Publisher American Chemical Society

Specialty Chemistry

Date 2009 Aug 12

PMID 19663433

Citations 12

Authors

Benjamin J Stokes

Kathleen J Richert

Tom G Driver

Affiliations

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Abstract

The use of a rhodium(II) carboxylate catalyst enables the mild and stereoselective formation of carbazoles from biaryl azides. Intramolecular competition experiments of triaryl azides suggested the source of the selectivity. A primary intramolecular kinetic isotope effect was not observed, and correlation of the product ratios with Hammett sigma(+) values produced a plot with two intersecting lines with opposite rho values. These data suggest that electronic donation by the biaryl pi-system accelerates the formation of rhodium nitrenoid and that C-N bond formation occurs through a 4pi-electron-5-atom electrocyclization.

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References

Moss R, Ma Y, Sauers R . A duality of mechanisms for the fragmentation of substituted benzyloxychlorocarbenes. J Am Chem Soc. 2002; 124(47):13968-9. DOI: 10.1021/ja0207605. View

Wolckenhauer S, Devlin A, Du Bois J . Delta-sultone formation through Rh-catalyzed C-H insertion. Org Lett. 2007; 9(21):4363-6. DOI: 10.1021/ol701950d. View

Moody C . Enantioselective insertion of metal carbenes into N-H bonds: a potentially versatile route to chiral amine derivatives. Angew Chem Int Ed Engl. 2007; 46(48):9148-50. DOI: 10.1002/anie.200703016. View

Burdzinski G, Gustafson T, Hackett J, Hadad C, Platz M . The direct detection of an aryl azide excited state: an ultrafast study of the photochemistry of para- and ortho-biphenyl azide. J Am Chem Soc. 2005; 127(40):13764-5. DOI: 10.1021/ja054135m. View

Liang C, Robert-Peillard F, Fruit C, Muller P, Dodd R, Dauban P . Efficient diastereoselective intermolecular rhodium-catalyzed C-H amination. Angew Chem Int Ed Engl. 2006; 45(28):4641-4. DOI: 10.1002/anie.200601248. View

Ragaini F, Penoni A, Gallo E, Tollari S, Li Gotti C, Lapadula M . Amination of benzylic C-H bonds by arylazides catalyzed by CoII-porphyrin complexes: a synthetic and mechanistic study. Chemistry. 2002; 9(1):249-59. DOI: 10.1002/chem.200390018. View

Hamilton C, Laitar D, Sadighi J . Oxidation-resistant, sterically demanding phenanthrolines as supporting ligands for copper(I) nitrene transfer catalysts. Chem Commun (Camb). 2004; (14):1628-9. DOI: 10.1039/b404515g. View

Lebel H, Huard K . De novo synthesis of Troc-protected amines: intermolecular rhodium-catalyzed C-H amination with N-tosyloxycarbamates. Org Lett. 2007; 9(4):639-42. DOI: 10.1021/ol062953t. View

Zdilla M, Dexheimer J, Abu-Omar M . Hydrogen atom transfer reactions of imido manganese(V) corrole: one reaction with two mechanistic pathways. J Am Chem Soc. 2007; 129(37):11505-11. DOI: 10.1021/ja073027s. View

10.

Arnold L, Guy R . Synthesis of highly substituted dibenzo[b,f]azocines and their evaluation as protein kinase inhibitors. Bioorg Med Chem Lett. 2006; 16(20):5360-3. DOI: 10.1016/j.bmcl.2006.07.078. View

11.

Ritleng V, Sirlin C, Pfeffer M . Ru-, Rh-, and Pd-catalyzed C-C bond formation involving C-H activation and addition on unsaturated substrates: reactions and mechanistic aspects. Chem Rev. 2002; 102(5):1731-70. DOI: 10.1021/cr0104330. View

12.

Thornton A, Blakey S . Catalytic metallonitrene/alkyne metathesis: a powerful cascade process for the synthesis of nitrogen-containing molecules. J Am Chem Soc. 2008; 130(15):5020-1. DOI: 10.1021/ja7111788. View

13.

Miura Y, Nishi T, Teki Y . Isolation and magnetic properties of heterocycle-carrying N-alkoxyarylaminyl radicals. J Org Chem. 2003; 68(26):10158-61. DOI: 10.1021/jo0302105. View

14.

Tsang W, Munday R, Brasche G, Zheng N, Buchwald S . Palladium-catalyzed method for the synthesis of carbazoles via tandem C-H functionalization and C-N bond formation. J Org Chem. 2008; 73(19):7603-10. PMC: 2748774. DOI: 10.1021/jo801273q. View

15.

Anada M, Washio T, Shimada N, Kitagaki S, Nakajima M, Shiro M . A new dirhodium(II) carboxamidate complex as a chiral Lewis acid catalyst for enantioselective hetero-Diels-Alder reactions. Angew Chem Int Ed Engl. 2008; 43(20):2665-8. DOI: 10.1002/anie.200453821. View

16.

Wong F, Wang J, Hengge A, Wu W . Mechanism of rhodium-catalyzed carbene formation from diazo compounds. Org Lett. 2007; 9(9):1663-5. DOI: 10.1021/ol070345n. View

17.

Wender P, Verma V, Paxton T, Pillow T . Function-oriented synthesis, step economy, and drug design. Acc Chem Res. 2007; 41(1):40-9. DOI: 10.1021/ar700155p. View

18.

Nowlan 3rd D, Gregg T, Davies H, Singleton D . Isotope effects and the nature of selectivity in rhodium-catalyzed cyclopropanations. J Am Chem Soc. 2003; 125(51):15902-11. DOI: 10.1021/ja036025q. View

19.

Stokes B, Dong H, Leslie B, Pumphrey A, Driver T . Intramolecular C-H amination reactions: exploitation of the Rh(2)(II)-catalyzed decomposition of azidoacrylates. J Am Chem Soc. 2007; 129(24):7500-1. DOI: 10.1021/ja072219k. View

20.

Hevia E, Perez J, Riera V, Miguel D . Insertion and cycloaddition reactivity of a transition-metal N-metalloimine. Angew Chem Int Ed Engl. 2002; 41(20):3858-60. DOI: 10.1002/1521-3773(20021018)41:20<3858::AID-ANIE3858>3.0.CO;2-J. View