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(NHC)CuH-Catalyzed Entry to Allenes via Propargylic Carbonate SN2′-Reductions

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Organic Chemistry, Dortmund University of Technology, Otto-Hahn-Strasse 6, D-44227 Dortmund, Germany, and Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106
[email protected]
†Dortmund University of Technology.
‡University of California, Santa Barbara.
Cite this: Org. Lett. 2009, 11, 21, 5010–5012
Publication Date (Web):October 5, 2009
https://doi.org/10.1021/ol901868m
Copyright © 2009 American Chemical Society
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    Abstract

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    The copper hydride-catalyzed SN2′-reduction of propargylic carbonates provides an efficient route to functionalized allenes. The method takes advantage of the stabilizing effect of NHC ligands on CuH and combines high reactivity and stereoselectivity with excellent tolerance toward reactive functionalities.

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    Experimental procedures and selected NMR spectra. This material is available free of charge via the Internet at http://pubs.acs.org.

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    5. Roscoe T. H. Linstadt, Carl. A. Peterson, Carina I. Jette, Zarko V. Boskovic, and Bruce H. Lipshutz . Control of Chemo-, Regio-, and Enantioselectivity in Copper Hydride Reductions of Morita–Baylis–Hillman Adducts. Organic Letters 2017, 19 (2) , 328-331. https://doi.org/10.1021/acs.orglett.6b03464
    6. Abraham J. Jordan, Gojko Lalic, and Joseph P. Sadighi . Coinage Metal Hydrides: Synthesis, Characterization, and Reactivity. Chemical Reviews 2016, 116 (15) , 8318-8372. https://doi.org/10.1021/acs.chemrev.6b00366
    7. T. N. Thanh Nguyen, Niklas O. Thiel, Felix Pape, and Johannes F. Teichert . Copper(I)-Catalyzed Allylic Substitutions with a Hydride Nucleophile. Organic Letters 2016, 18 (10) , 2455-2458. https://doi.org/10.1021/acs.orglett.6b00941
    8. Aaron M Whittaker and Gojko Lalic . Monophasic Catalytic System for the Selective Semireduction of Alkynes. Organic Letters 2013, 15 (5) , 1112-1115. https://doi.org/10.1021/ol4001679
    9. Mingyu Yang, Natsumi Yokokawa, Hirohisa Ohmiya, and Masaya Sawamura . Synthesis of Conjugated Allenes through Copper-Catalyzed γ-Selective and Stereospecific Coupling between Propargylic Phosphates and Aryl- or Alkenylboronates. Organic Letters 2012, 14 (3) , 816-819. https://doi.org/10.1021/ol2033465
    10. Hirohisa Ohmiya, Umi Yokobori, Yusuke Makida, and Masaya Sawamura . General Approach to Allenes through Copper-Catalyzed γ-Selective and Stereospecific Coupling between Propargylic Phosphates and Alkylboranes. Organic Letters 2011, 13 (23) , 6312-6315. https://doi.org/10.1021/ol202866h
    11. Devendra J. Vyas, Chinmoy K. Hazra, and Martin Oestreich . Copper(I)-Catalyzed Regioselective Propargylic Substitution Involving Si–B Bond Activation. Organic Letters 2011, 13 (16) , 4462-4465. https://doi.org/10.1021/ol201811d
    12. Nicole J. Rijs and Richard A. J. O’Hair . Unimolecular Reactions of Organocuprates and Organoargentates. Organometallics 2010, 29 (10) , 2282-2291. https://doi.org/10.1021/om1000875
    13. Guojing Pei, Hui Chen, Wan Xu, Tao Chen, Juan Li. Diboron-controlled product selectivity switch in copper-catalyzed decarboxylative substitutions of alkynyl cyclic carbonates. Organic Chemistry Frontiers 2021, 8 (24) , 6950-6961. https://doi.org/10.1039/D1QO01411K
    14. B. Cornils. IBiox. 2020https://doi.org/10.1002/9783527809080.cataz08714
    15. Yifan Jiang, Yangyang Ma, Enlu Ma, Zhiping Li. Copper‐Catalyzed Selective Cross‐Couplings of Propargylic Ethers with Aryl Grignard Reagents. Asian Journal of Organic Chemistry 2019, 8 (10) , 1834-1837. https://doi.org/10.1002/ajoc.201900409
    16. Jung Tae Han, Jaesook Yun. Asymmetric synthesis of α-chiral β-hydroxy allenes: copper-catalyzed γ-selective borylative coupling of vinyl arenes and propargyl phosphates. Chemical Communications 2019, 55 (66) , 9813-9816. https://doi.org/10.1039/C9CC04165F
    17. T. N. Thanh Nguyen, Niklas O. Thiel, Johannes F. Teichert. Copper( i )-catalysed asymmetric allylic reductions with hydrosilanes. Chem. Commun. 2017, 53 (85) , 11686-11689. https://doi.org/10.1039/C7CC07008J
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    19. Theresa M. Locascio, Jon A. Tunge. Palladium-Catalyzed Regiodivergent Substitution of Propargylic Carbonates. Chemistry - A European Journal 2016, 22 (50) , 18140-18146. https://doi.org/10.1002/chem.201603481
    20. Jérôme M. Lavis, Robert E. Maleczka, Vijayanand Chandrasekaran, Steven J. Collier. Polymethylhydrosiloxane. 2016, 1-20. https://doi.org/10.1002/047084289X.rn00062.pub2
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    24. Faïma Lazreg, Fady Nahra, Catherine S.J. Cazin. Copper–NHC complexes in catalysis. Coordination Chemistry Reviews 2015, 293-294 , 48-79. https://doi.org/10.1016/j.ccr.2014.12.019
    25. Faïma Lazreg, Catherine S. J. Cazin. NHC–Copper Complexes and their Applications. 2014, 199-242. https://doi.org/10.1002/9783527671229.ch08
    26. Bruce H. Lipshutz. Organocopper Chemistry. 2013, 1-133. https://doi.org/10.1002/9781118651421.ch1
    27. Tse-Lok Ho, Mary Fieser, Louis Fieser. Aminocarbene-Metal Complexes. 2013https://doi.org/10.1002/9780471264194.fos11693.pub2
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    39. Nicolas Marion*. NHC–Copper, Silver and Gold Complexes in Catalysis. 2010, 317-344. https://doi.org/10.1039/9781849732161-00317
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    44. Carl Deutsch, Bruce H. Lipshutz, Norbert Krause. ChemInform Abstract: (NHC)CuH-Catalyzed Entry to Allenes via Propargylic Carbonate S N 2′-Reductions.. ChemInform 2010, 41 (10) https://doi.org/10.1002/chin.201010064
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