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. 2014 Jul 1;53(27):7028-32.
doi: 10.1002/anie.201400557. Epub 2014 May 19.

Chemoselective amination of propargylic C(sp³)-H bonds by cobalt(II)-based metalloradical catalysis

Hongjian Lu  1 , Chaoqun Li, Huiling Jiang, Christopher L Lizardi, X Peter Zhang
Affiliations

Chemoselective amination of propargylic C(sp³)-H bonds by cobalt(II)-based metalloradical catalysis

Hongjian Lu et al. Angew Chem Int Ed Engl. .

Abstract

Highly chemoselective intramolecular amination of propargylic C(sp(3))-H bonds has been demonstrated for N-bishomopropargylic sulfamoyl azides through cobalt(II)-based metalloradical catalysis. Supported by D(2h)-symmetric amidoporphyrin ligand 3,5-Di(t)Bu-IbuPhyrin, the cobalt(II)-catalyzed C-H amination proceeds effectively under neutral and nonoxidative conditions without the need of any additives, and generates N2 as the only byproduct. The metalloradical amination is suitable for both secondary and tertiary propargylic C-H substrates with an unusually high degree of functional-group tolerance, thus providing a direct method for high-yielding synthesis of functionalized propargylamine derivatives.

Keywords: alkynes; chemoselectivity; cobalt; heterocycles; homogeneous catalysis.

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Figures

Scheme 1
Scheme 1
Synthesis of Propargylamines via Catalytic C–H Amination.
Scheme 2
Scheme 2
Ligand Effect on [Co(Por)]-Catalyzed Intramolecular Propargylic C–H Amination of Sulfamoyl Azide.
Scheme 3
Scheme 3
Application of Catalytic Propargylic C–H Amination for Deoxyuridine-Based Sulfamoyl Azide.
Scheme 4
Scheme 4
Ring-Opening Reaction for Generation of 1,3-Propargylic Diamine with Different Protecting Groups.
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References

    1. Selected examples: Nilsson B, Vargas HM, Ringdahl B, Hacksell U. J Med Chem. 1992;35:285–294.Jenmalm A, Berts W, Li YL, Luthman K, Csoeregh I, Hacksell U. J Org Chem. 1994;59:1139–1148.Miura M, Enna M, Okuro K, Nomura M. J Org Chem. 1995;60:4999–5004.Davidson MH, McDonald FE. Org Lett. 2004;6:1601–1603.Trost BM, Chung CK, Pinkerton AB. Angew Chem. 2004;116:4427–4429.Angew Chem Int Ed. 2004;43:4327–4329.Nakamura H, Kamakura T, Ishikura M, Biellmann JF. J Am Chem Soc. 2004;126:5958–5959.Detz RJ, Abiri Z, le Griel R, Hiemstra H, van Maarseveen JH. Chem Eur J. 2011;17:5921–5930.Ding CH, Hou XL. Chem Rev. 2011;111:1914–1937.Aubert C, Buisine O, Malacria M. Chem Rev. 2002;102:813–834.Naota T, Takaya H, Murahashi SI. Chem Rev. 1998;98:2599–2660.

    1. Konishi M, Ohkuma H, Tsuno T, Oki T, Vanduyne GD, Clardy J. J Am Chem Soc. 1990;112:3715–3716.
    2. Yu PH, Davis BA, Boulton AA. J Med Chem. 1992;35:3705–3713. - PubMed
    3. Huffman MA, Yasuda N, Decamp AE, Grabowski EJJ. J Org Chem. 1995;60:1590–1594.
    4. Enders D, Reinhold U. Tetrahedron-Asymmetry. 1997;8:1895–1946.
    5. Kauffman GS, Harris GD, Dorow RL, Stone BRP, Parsons RL, Pesti JA, Magnus NA, Fortunak JM, Confalone PN, Nugent WA. Org Lett. 2000;2:3119–3121. - PubMed
    1. Aubrecht KB, Winemiller MD, Collum DB. J Am Chem Soc. 2000;122:11084–11089.
    2. Tuulmets A, Pallin V, Tammiku-Taul J, Burk P, Raie K. J Phys Org Chem. 2002;15:701–705.
    3. Murai T, Ohta Y, Mutoh Y. Tetrahedron Lett. 2005;46:3637–3640.
    4. Ma Y, Lobkovsky E, Collum DB. J Org Chem. 2005;70:2335–2337. - PubMed
    5. Magueur G, Crousse B, Bonnet-Delpon D. Tetrahedron Lett. 2005;46:2219–2221.
    6. Ding CH, Chen DD, Luo ZB, Dai LX, Hou XL. Synlett. 2006:1272–1274.
    7. Badorrey R, Diaz-de-Villegas MD, Diez R, Galvez JA. Eur J Org Chem. 2007:2114–2120.
    8. Wee AGH, Zhang B. Tetrahedron Lett. 2007;48:4135–4138.

    1. For recent reviews on “A3-coupling”, see: Peshkov VA, Pereshivko OP, Van der Eycken EV. Chem Soc Rev. 2012;41:3790–3807.Yoo WJ, Zhao L, Li CJ. Aldrichimica Acta. 2011;44:43–51.Li CJ. Acc Chem Res. 2010;43:581–590.Kouznetsov VV, Méndez LYV. Synthesis. 2008;4:491–506.Zani L, Bolm C. Chem Commun. 2006:4263–4275.Wei CM, Li ZG, Li CJ. Synlett. 2004:1472–1483.

    1. For synthesis of propargylamines through alkynylation of C–H bonds adjacent to nitrogen atoms of existing amines, see: Li ZP, Li CJ. Org Lett. 2004;6:4997–4999.Li ZP, Li CJ. J Am Chem Soc. 2004;126:11810–11811.Niu M, Yin Z, Fu H, Jiang Y, Zhao Y. J Org Chem. 2008;73:3961–3963.Detz RJ, Abiri Z, le Griel R, Hiemstra H, van Maarseveen JH. Chem-Eur J. 2011;17:5921–5930.Sugiishi T, Nakamura H. J Am Chem Soc. 2012;134:2504–2507.

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