ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Preorganized Hydrogen Bond Donor Catalysts: Acidities and Reactivities

View Author Information
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455, United States
Cite this: J. Org. Chem. 2015, 80, 15, 7727–7731
Publication Date (Web):July 3, 2015
https://doi.org/10.1021/acs.joc.5b01475
Copyright © 2015 American Chemical Society

    Article Views

    1101

    Altmetric

    -

    Citations

    LEARN ABOUT THESE METRICS
    Other access options
    Supporting Info (1)»

    Abstract

    Abstract Image

    Measured DMSO pKa values for a series of rigid tricyclic adamantane-like triols containing 0–3 trifluoromethyl groups (i.e., 3(0)3(3)) are reported. The three compounds with CF3 substituents are similar or more acidic than acetic acid (pKa = 13.5 (3(1)), 9.5 (3(2)), 7.3 (3(3)) vs 12.6 (HOAc)), and the resulting hydrogen bond network enables a remote γ-trifluoromethyl group to enhance the acidity as well as one located at the α-position. Catalytic abilities of 3(0)3(3) were also examined. In a nonpolar environment a rate enhancement of up to 100-fold over flexible acyclic analogs was observed presumably due to an entropic advantage of the locked-in structure. Gas-phase acidities are found to correlate with the catalytic activity better than DMSO pKa values and appear to be a better measure of acidities in low dielectric constant media. These trends are reduced or reversed in polar solvents highlighting the importance of the reaction environment.

    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. You can change your affiliated institution below.

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    Kinetic data, estimated acidities, and computed geometries and energies are provided along with the complete citation to ref 49. The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.joc.5b01475.

    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

    This article is cited by 18 publications.

    1. Mathieu Morency, Sébastien Néron, Radu Iftimie, James D. Wuest. Predicting pKa Values of Quinols and Related Aromatic Compounds with Multiple OH Groups. The Journal of Organic Chemistry 2021, 86 (21) , 14444-14460. https://doi.org/10.1021/acs.joc.1c01279
    2. Zena M. Salem, Jason Saway, Joseph J. Badillo. Photoacid-Catalyzed Friedel–Crafts Arylation of Carbonyls. Organic Letters 2019, 21 (21) , 8528-8532. https://doi.org/10.1021/acs.orglett.9b02841
    3. Kayla M. Diemoz, Annaliese K. Franz. NMR Quantification of Hydrogen-Bond-Activating Effects for Organocatalysts including Boronic Acids. The Journal of Organic Chemistry 2019, 84 (3) , 1126-1138. https://doi.org/10.1021/acs.joc.8b02389
    4. Yang Fan, Curtis Payne, Steven R. Kass. Quantification of Catalytic Activity for Electrostatically Enhanced Thioureas via Reaction Kinetics and UV–vis Spectroscopic Measurement. The Journal of Organic Chemistry 2018, 83 (18) , 10855-10863. https://doi.org/10.1021/acs.joc.8b01552
    5. Kayla M. Diemoz, Jason E. Hein, Sean O. Wilson, James C. Fettinger, and Annaliese K. Franz . Reaction Progress Kinetics Analysis of 1,3-Disiloxanediols as Hydrogen-Bonding Catalysts. The Journal of Organic Chemistry 2017, 82 (13) , 6738-6747. https://doi.org/10.1021/acs.joc.7b00875
    6. Evgeny V. Beletskiy, Xue-Bin Wang, and Steven R. Kass . Anion Binding of One-, Two-, and Three-Armed Thiourea Receptors Examined via Photoelectron Spectroscopy and Quantum Computations. The Journal of Physical Chemistry A 2016, 120 (42) , 8309-8316. https://doi.org/10.1021/acs.jpca.6b08438
    7. Khetpakorn Chakarawet, Ioana Knopf, Matthew Nava, Yanfeng Jiang, Julia M. Stauber, and Christopher C. Cummins . Crystalline Metaphosphate Acid Salts: Synthesis in Organic Media, Structures, Hydrogen-Bonding Capability, and Implication of Superacidity. Inorganic Chemistry 2016, 55 (12) , 6178-6185. https://doi.org/10.1021/acs.inorgchem.6b00749
    8. Yang Fan and Steven R. Kass . Electrostatically Enhanced Thioureas. Organic Letters 2016, 18 (2) , 188-191. https://doi.org/10.1021/acs.orglett.5b03213
    9. Stefan H. Jungbauer and Stefan M. Huber . Cationic Multidentate Halogen-Bond Donors in Halide Abstraction Organocatalysis: Catalyst Optimization by Preorganization. Journal of the American Chemical Society 2015, 137 (37) , 12110-12120. https://doi.org/10.1021/jacs.5b07863
    10. Saket Jain, Saurabh Sandip Satpute, Raushan Kumar Jha, Mili Sanjeev Patel, Sangit Kumar. Bidentate Ligand Driven Intramolecularly Te…O Bonded Organotellurium Cations from Synthesis, Stability to Catalysis. Chemistry – A European Journal 2023, 36 https://doi.org/10.1002/chem.202303089
    11. Adrien Quintard. Copper Catalyzed Decarboxylative Functionalization of Ketoacids. The Chemical Record 2021, 21 (12) , 3382-3393. https://doi.org/10.1002/tcr.202100045
    12. Céline Sperandio, Jean Rodriguez, Adrien Quintard. Development of copper-catalyzed enantioselective decarboxylative aldolization for the preparation of perfluorinated 1,3,5-triols featuring supramolecular recognition properties. Chemical Science 2020, 11 (6) , 1629-1635. https://doi.org/10.1039/C9SC05196A
    13. Céline Sperandio, Guilhem Quintard, Jean‐Valere Naubron, Michel Giorgi, Mehdi Yemloul, Jean‐Luc Parrain, Jean Rodriguez, Adrien Quintard. Strategic Stereoselective Halogen (F, Cl) Insertion: A Tool to Enhance Supramolecular Properties in Polyols. Chemistry – A European Journal 2019, 25 (66) , 15098-15105. https://doi.org/10.1002/chem.201902983
    14. Truong Nguyen, Po-An Chen, Krit Setthakarn, Jeremy May. Chiral Diol-Based Organocatalysts in Enantioselective Reactions. Molecules 2018, 23 (9) , 2317. https://doi.org/10.3390/molecules23092317
    15. Chen Yang, Jie Wang, Yang Liu, Xiang Ni, Xin Li, Jin‐Pei Cheng. Study on the Catalytic Behavior of Bifunctional Hydrogen‐Bonding Catalysts Guided by Free Energy Relationship Analysis of Steric Parameters. Chemistry – A European Journal 2017, 23 (23) , 5488-5497. https://doi.org/10.1002/chem.201605666
    16. Andrej Emanuel Cotman, Dominique Cahard, Barbara Mohar. Stereoarrayed CF 3 ‐Substituted 1,3‐Diols by Dynamic Kinetic Resolution: Ruthenium(II)‐Catalyzed Asymmetric Transfer Hydrogenation. Angewandte Chemie 2016, 128 (17) , 5380-5384. https://doi.org/10.1002/ange.201600812
    17. Andrej Emanuel Cotman, Dominique Cahard, Barbara Mohar. Stereoarrayed CF 3 ‐Substituted 1,3‐Diols by Dynamic Kinetic Resolution: Ruthenium(II)‐Catalyzed Asymmetric Transfer Hydrogenation. Angewandte Chemie International Edition 2016, 55 (17) , 5294-5298. https://doi.org/10.1002/anie.201600812
    18. Xiang Ni, Xin Li, Zhen Li, Jin-Pei Cheng. Equilibrium acidities of BINOL type chiral phenolic hydrogen bonding donors in DMSO. Organic Chemistry Frontiers 2016, 3 (9) , 1154-1158. https://doi.org/10.1039/C6QO00252H

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    MENDELEY PAIRING EXPIRED
    Your Mendeley pairing has expired. Please reconnect