Intramolecular Ir(I)-catalyzed benzylic C-H bond amination of ortho-substituted aryl azides

doi:10.1021/ol901317j

. 2009 Aug 20;11(16):3598-601.

doi: 10.1021/ol901317j.

Intramolecular Ir(I)-catalyzed benzylic C-H bond amination of ortho-substituted aryl azides

Ke Sun¹, Rachna Sachwani, Kathleen J Richert, Tom G Driver

Affiliations

PMID: 19627144
PMCID: PMC2743533
DOI: 10.1021/ol901317j

Intramolecular Ir(I)-catalyzed benzylic C-H bond amination of ortho-substituted aryl azides

Ke Sun et al. Org Lett. 2009.

. 2009 Aug 20;11(16):3598-601.

doi: 10.1021/ol901317j.

Authors

Ke Sun¹, Rachna Sachwani, Kathleen J Richert, Tom G Driver

Affiliation

¹ Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, Illinois 60607-7061, USA.

PMID: 19627144
PMCID: PMC2743533
DOI: 10.1021/ol901317j

Abstract

Iridium(I) catalyzes the intramolecular benzylic C-H bond amination of ortho-homobenzyl-substituted aryl azides to produce indolines at 25 degrees C.

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Figures

**Scheme 1**
Comparison of Catalytic Efficieny of Ir(I) versus Rh(II) for Aromatic N-Heterocycle Formation.

**Scheme 2**
Intermolecular Competition Experiments.

**Scheme 3**
Potential Mechanism for Benzylic C–H Amination.

See this image and copyright information in PMC

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References

1. Cho J-Y, Tse MK, Holmes D, Maleczka RE, Jr, Smith MR., III Science. 2002;295:305. - PubMed
2. Ishiyama T, Takagi J, Ishida K, Miyaura N, Anastasi NR, Hartwig JF. J Am Chem Soc. 2002;124:390. - PubMed
3. Lu B, Falck JR. Angew Chem, Int Ed. 2008;47:7508. - PMC - PubMed
1. Ir-catalysts were found to be significantly less reactive than the corresponding Rh-complexes, see: Chen H, Schlecht S, Semple TC, Hartwig JF. Science. 2000;287:1995.Shimada S, Batsanov AS, Howard JAK, Marder TB. Angew Chem, Int Ed. 2001;40:2168.
1. Collman JP, Kubota M, Vastine FD, Sun JY, Kang JW. J Am Chem Soc. 1968;90:5430.
2. Basolo F, Lane BC, McDonald John W, Myers VG, Pearson RG. J Am Chem Soc. 1971;93:4934.
3. Johnson ED, Basolo F. Inorg Chem. 1977;16:554.
1. Reviews of aliphatic C–H bond functionalization: Labinger JA, Bercaw JE. Nature. 2002;417:507.Du Bois J. Chemtracts. 2005;18:1.Godula K, Sames D. Science. 2006;312:67.Dick AR, Sanford MS. Tetrahedron. 2006;62:2439.Davies HML, Manning JR. Nature. 2008;451:417.
1. For recent, leading reports of related Pd-catalyzed C–H aminations, see: Thu HY, Yu WY, Che CM. J Am Chem Soc. 2006;128:9048.Fraunhoffer KJ, White MC. J Am Chem Soc. 2007;129:7274.Tsang WCP, Munday RH, Brasche G, Zheng N, Buchwald SL. J Org Chem. 2008;73:7603.Jordan-Hore JA, Johansson CCC, Gulias M, Beck EM, Gaunt MJ. J Am Chem Soc. 2008;130:16184.

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[1] Cho J-Y, Tse MK, Holmes D, Maleczka RE, Jr, Smith MR., III Science. 2002;295:305. - PubMed

Ishiyama T, Takagi J, Ishida K, Miyaura N, Anastasi NR, Hartwig JF. J Am Chem Soc. 2002;124:390. - PubMed

Lu B, Falck JR. Angew Chem, Int Ed. 2008;47:7508. - PMC - PubMed

[2] Cho J-Y, Tse MK, Holmes D, Maleczka RE, Jr, Smith MR., III Science. 2002;295:305. - PubMed

[3] Ishiyama T, Takagi J, Ishida K, Miyaura N, Anastasi NR, Hartwig JF. J Am Chem Soc. 2002;124:390. - PubMed

[4] Lu B, Falck JR. Angew Chem, Int Ed. 2008;47:7508. - PMC - PubMed

[5] Ir-catalysts were found to be significantly less reactive than the corresponding Rh-complexes, see: Chen H, Schlecht S, Semple TC, Hartwig JF. Science. 2000;287:1995.Shimada S, Batsanov AS, Howard JAK, Marder TB. Angew Chem, Int Ed. 2001;40:2168.

[6] Ir-catalysts were found to be significantly less reactive than the corresponding Rh-complexes, see: Chen H, Schlecht S, Semple TC, Hartwig JF. Science. 2000;287:1995.Shimada S, Batsanov AS, Howard JAK, Marder TB. Angew Chem, Int Ed. 2001;40:2168.

[7] Collman JP, Kubota M, Vastine FD, Sun JY, Kang JW. J Am Chem Soc. 1968;90:5430.

Basolo F, Lane BC, McDonald John W, Myers VG, Pearson RG. J Am Chem Soc. 1971;93:4934.

Johnson ED, Basolo F. Inorg Chem. 1977;16:554.

[8] Collman JP, Kubota M, Vastine FD, Sun JY, Kang JW. J Am Chem Soc. 1968;90:5430.

[9] Basolo F, Lane BC, McDonald John W, Myers VG, Pearson RG. J Am Chem Soc. 1971;93:4934.

[10] Johnson ED, Basolo F. Inorg Chem. 1977;16:554.

[11] Reviews of aliphatic C–H bond functionalization: Labinger JA, Bercaw JE. Nature. 2002;417:507.Du Bois J. Chemtracts. 2005;18:1.Godula K, Sames D. Science. 2006;312:67.Dick AR, Sanford MS. Tetrahedron. 2006;62:2439.Davies HML, Manning JR. Nature. 2008;451:417.

[12] Reviews of aliphatic C–H bond functionalization: Labinger JA, Bercaw JE. Nature. 2002;417:507.Du Bois J. Chemtracts. 2005;18:1.Godula K, Sames D. Science. 2006;312:67.Dick AR, Sanford MS. Tetrahedron. 2006;62:2439.Davies HML, Manning JR. Nature. 2008;451:417.

[13] For recent, leading reports of related Pd-catalyzed C–H aminations, see: Thu HY, Yu WY, Che CM. J Am Chem Soc. 2006;128:9048.Fraunhoffer KJ, White MC. J Am Chem Soc. 2007;129:7274.Tsang WCP, Munday RH, Brasche G, Zheng N, Buchwald SL. J Org Chem. 2008;73:7603.Jordan-Hore JA, Johansson CCC, Gulias M, Beck EM, Gaunt MJ. J Am Chem Soc. 2008;130:16184.

[14] For recent, leading reports of related Pd-catalyzed C–H aminations, see: Thu HY, Yu WY, Che CM. J Am Chem Soc. 2006;128:9048.Fraunhoffer KJ, White MC. J Am Chem Soc. 2007;129:7274.Tsang WCP, Munday RH, Brasche G, Zheng N, Buchwald SL. J Org Chem. 2008;73:7603.Jordan-Hore JA, Johansson CCC, Gulias M, Beck EM, Gaunt MJ. J Am Chem Soc. 2008;130:16184.

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Intramolecular Ir(I)-catalyzed benzylic C-H bond amination of ortho-substituted aryl azides

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Intramolecular Ir(I)-catalyzed benzylic C-H bond amination of ortho-substituted aryl azides

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