ACS Publications. Most Trusted. Most Cited. Most Read
Regioselective Anti-Silyllithiation of Propargylic Alcohols
My Activity
    Featured Article

    Regioselective Anti-Silyllithiation of Propargylic Alcohols
    Click to copy article linkArticle link copied!

    Other Access OptionsSupporting Information (1)

    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2024, 89, 6, 3677–3683
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.joc.2c01795
    Published November 7, 2022
    Copyright © 2022 American Chemical Society

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    Among the known hydrosilylation or carbosilylation conditions of alkynes, anti-addition of the two units across the triple bond is considered rare compared to the syn counterpart. For anti-silylative vicinal difunctionalizations, transition-metal catalysts, such as ruthenium or palladium complexes, are generally required. Accordingly, silyl alkali metals have not been employed for those anti-addition transformations. Here we demonstrate that silyllithiums can add across the triple bond of a series of propargylic alkoxides regioselectively in an anti-fashion. Upon treatment with a variety of electrophiles, the trisubstituted alkenyl lithium intermediates were transformed into highly functionalized β-silyl allylic alcohols with high regiocontrol, eventually providing tri- or tetrasubstituted alkenylsilanes stereoselectively. A classic trick for anti-addition with propargylic alkoxides has transformed anti-silylative functionalizations into a robust and reliable strategy.

    Copyright © 2022 American Chemical Society

    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.

    Supporting Information

    Click to copy section linkSection link copied!

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.joc.2c01795.

    • Experimental procedures, computational data, and characterization and spectral data for new compounds (PDF)

    Accession Codes

    CCDC 2153783 and 21537942153795 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

    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

    This article is cited by 2 publications.

    1. Xueyao Mu, Shuai Peng, Fangyao Su, Shuting Yin, Yongguo Liu, Baoguo Sun, Hongyu Tian, Sen Liang. Hydromethylthiolation of alkynes via nucleophilic addition of dimethyl disulfide in DMSO. Journal of Molecular Structure 2025, 1321 , 140226. https://doi.org/10.1016/j.molstruc.2024.140226
    2. Tomohiko Sato, Somnath N. Karad, Jun Shimokawa, Hideki Yorimitsu. Regioselective anti-Silyllithiation of Propargylic Amines. Synlett 2024, 35 (04) , 419-422. https://doi.org/10.1055/a-2047-8456

    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2024, 89, 6, 3677–3683
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.joc.2c01795
    Published November 7, 2022
    Copyright © 2022 American Chemical Society

    Article Views

    3253

    Altmetric

    -

    Citations

    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.