ACS Publications. Most Trusted. Most Cited. Most Read
Asymmetric Addition of an Electrophile to Naphthalenes Promoted and Stereodirected by Alcohol

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Am. Chem. Soc. 2001, 123, 13, 2946-2957
    Article

    Asymmetric Addition of an Electrophile to Naphthalenes Promoted and Stereodirected by Alcohol
    Click to copy article linkArticle link copied!

    View Author Information
    Contribution from the Faculty of Science, Himeji Institute of Technology, Kouto, Kamigori, Ako-gun, Hyogo 678-1297, Japan
    Other Access OptionsSupporting Information (2)

    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2001, 123, 13, 2946–2957
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ja0029477
    Published March 8, 2001
    Copyright © 2001 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!

    4-Phenyl-1,2,4-triazoline-3,5-dione (PTAD) reacts with 1-methoxy-4-methylnaphthalene to give the 1,4-addition product in the presence of methanol; the reaction does not proceed in the absence of the alcohol. Methoxy exchange (with CD3OD) was also observed during the reaction. Reactions of PTAD with 1-(3-hydroxypropoxy)-4-methylnaphthalene and related naphthalenes afford stereoselectively 1,4-adducts (70−98% of the major diastereomer). The stereoface-selective addition of PTAD at C-4 with concurrent formation of an acetal at C-1 takes place in a syn manner, which is induced by the hydrogen-bonding interaction between PTAD and the hydroxy group. The α-methyl substitution on the propoxy side chain strongly enhances the stereodifferentiation (90% de) and accelerates the cyclization by the Thorpe−Ingold effect. The alkoxy moiety of the adduct is easily removed to give 4-methyl-4-amino-4H-naphthalen-1-one with high enantiomeric excess. The γ-methyl group of the side chain also affects the stereodifferentiation. Thus, the two stereogenic centers of the (1S,3R)-3-hydroxy-1-methylbutoxy side chain work together to achieve the high stereodifferentiating 1,4-addition from the Si-Re face (up to 96% ee). Epimerization of the cyclic acetal of a minor adduct was observed during the reaction of 1-(3-hydroxybutoxy)-4-methylnaphthalene, indicating that the minor component of the final products is derived from the initial minor syn adduct formed from the opposite face. The syn selectivity of the addition is achieved completely in the initial stage of formation of both the major and the minor adducts.

    Copyright © 2001 American Chemical Society

    Subjects

    what are subjects

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    *

    In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

    †

     E-mail:  [email protected].

    Supporting Information Available

    Click to copy section linkSection link copied!

    Detailed spectral data. This material is available free charge via the Internet at http://pubs.acs.org.

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai
    powered by  Scite

    This article is cited by 18 publications.

    1. Aika Yanagimoto, Masaaki Komatsuda, Kei Muto, Junichiro Yamaguchi. Dearomative Allylation of Naphthyl Cyanohydrins by Palladium Catalysis: Catalyst-Enhanced Site Selectivity. Organic Letters 2020, 22 (9) , 3423-3427. https://doi.org/10.1021/acs.orglett.0c00897
    2. Masaaki Komatsuda, Hiroki Kato, Kei Muto, Junichiro Yamaguchi. Pd-Catalyzed Dearomative Three-Component Reaction of Bromoarenes with Diazo Compounds and Allylborates. ACS Catalysis 2019, 9 (10) , 8991-8995. https://doi.org/10.1021/acscatal.9b03461
    3. Dustin Kaiser, Johan M. Winne, Maria Elena Ortiz-Soto, Jürgen Seibel, Thien A. Le, Bernd Engels. Mechanistical Insights into the Bioconjugation Reaction of Triazolinediones with Tyrosine. The Journal of Organic Chemistry 2018, 83 (17) , 10248-10260. https://doi.org/10.1021/acs.joc.8b01445
    4. Masaaki Komatsuda, Kei Muto, Junichiro Yamaguchi. Pd-Catalyzed Dearomative Allylation of Benzyl Phosphates. Organic Letters 2018, 20 (14) , 4354-4357. https://doi.org/10.1021/acs.orglett.8b01807
    5. Katsumasa Kamiya, Toru Matsui, Takashi Sugimura, and Yasuteru Shigeta . Theoretical Insight into Stereoselective Reaction Mechanisms of 2,4-Pentanediol-Tethered Ketene-Olefin [2 + 2] Cycloaddition. The Journal of Physical Chemistry A 2012, 116 (4) , 1168-1175. https://doi.org/10.1021/jp211542m
    6. Mariza N. Alberti and Michael Orfanopoulos. Concerning the Reactivity of PTAD with Isomeric Dienes: The Mechanism of the Diels−Alder Cycloaddition. Organic Letters 2009, 11 (7) , 1659-1662. https://doi.org/10.1021/ol900363n
    7. Fernando López Ortiz,, María José Iglesias,, Ignacio Fernández,, Carmen M. Andújar Sánchez, and, Gloria Ruiz Gómez. Nucleophilic Dearomatizing (DNAr) Reactions of Aromatic C,H-Systems. A Mature Paradigm in Organic Synthesis. Chemical Reviews 2007, 107 (5) , 1580-1691. https://doi.org/10.1021/cr030207l
    8. Mark T. Valahovic,, William H. Myers, and, W. Dean Harman. Discrimination of Enantiofaces and Stereoselective Electrophilic Addition Reactions for η2-Pyrrole Complexes. Organometallics 2002, 21 (22) , 4581-4589. https://doi.org/10.1021/om020606r
    9. Mark T. Valahovic,, T. Brent Gunnoe,, Michal Sabat, and, W. Dean Harman. Ligand-Modulated Stereo- and Regioselective Tandem Addition Reactions of Rhenium-Bound Naphthalene. Journal of the American Chemical Society 2002, 124 (13) , 3309-3315. https://doi.org/10.1021/ja012066f
    10. Liu Zhao, Shi‐Jun Li, De‐Cai Fang. A Theoretical Study of Ene Reactions in Solution: A Solution‐Phase Translational Entropy Model. ChemPhysChem 2015, 16 (17) , 3711-3718. https://doi.org/10.1002/cphc.201500662
    11. Vladimir D. Kiselev, Dmitry A. Kornilov, Helen A. Kashaeva, Lyubov N. Potapova, Alexander I. Konovalov. 4‐Phenyl‐1,2,4‐triazoline‐3,5‐dione in the ene reactions with cyclohexene, 1‐hexene and 2,3‐dimethyl‐2‐butene. The heat of reaction and the influence of temperature and pressure on the reaction rate. Journal of Physical Organic Chemistry 2014, 27 (5) , 401-406. https://doi.org/10.1002/poc.3277
    12. Hans-Joachim Lehmler, Huimin Wu, Sean Parkin. 2,2′,5′,6-Tetrachloro-4-[(1 S )-1-methylpropoxy]biphenyl. Acta Crystallographica Section E Structure Reports Online 2013, 69 (6) , o983-o983. https://doi.org/10.1107/S1600536813014098
    13. Takashi Sugimura, Eigo Mitani, Takahiro Tei, Tadashi Okuyama, Katsumasa Kamiya, Toru Matsui, Yasuteru Shigeta. Temperature-Independent Stereoselectivity in Intramolecular Cycloaddition of Ketene Generated from Diazoester in Solution and in Vapor Phase: How Entropy Term Governs the Selectivity. Bulletin of the Chemical Society of Japan 2012, 85 (4) , 504-510. https://doi.org/10.1246/bcsj.20110337
    14. Abel Ros, Antonio Bermejo, Varinder K. Aggarwal. Benzylic Boron Reagents Behaving as Allylic Boron Reagents towards Aldehydes: A New Asymmetric Reaction Leading to Homoallylic Alcohols with Concomitant Dearomatisation. Chemistry – A European Journal 2010, 16 (32) , 9741-9745. https://doi.org/10.1002/chem.201001174
    15. Amanda L. Jones, John K. Snyder. Synthesis of Unique Scaffolds via Diels−Alder Cycloadditions of Tetrasubstituted Cyclohexadienes. Organic Letters 2010, 12 (7) , 1592-1595. https://doi.org/10.1021/ol100318f
    16. Takashi Sugimura. Entropy‐Driven Asymmetric Synthesis with Chiral Tethers. European Journal of Organic Chemistry 2004, 2004 (6) , 1185-1192. https://doi.org/10.1002/ejoc.200300518
    17. Takashi Sugimura, Chun Young Im, Tadashi Okuyama. [6+2] Cycloaddition of N -phenyltriazolinedione with cycloheptatriene derivatives mediated and stereodirected by a chiral 3-oxy substituent. Tetrahedron Letters 2004, 45 (7) , 1519-1521. https://doi.org/10.1016/j.tetlet.2003.12.044
    18. Takashi Sugimura, Takahiro Tei, Tadashi Okuyama. Asymmetric synthesis by vapor phase pyrolysis. Tetrahedron Letters 2003, 44 (15) , 3115-3117. https://doi.org/10.1016/S0040-4039(03)00549-5
    Download PDF
    Go to Journal of the American Chemical Society
    Get e-Alerts
    Get e-Alerts

    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2001, 123, 13, 2946–2957
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ja0029477
    Published March 8, 2001
    Copyright © 2001 American Chemical Society
    Request reuse permissions

    Article Views

    1051

    Altmetric

    -

    Citations

    18
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.