Electron transfer and hydride transfer pathways in the Stoltz-Grubbs reducing system (KOtBu-Et3SiH)

Smith, Andrew J. and Young, Allan and Rohrbach, Simon and O'Connor, Erin F. and Allison, Mark and Wang, Hong-Shuang and Poole, Darren L. and Tuttle, Tell and Murphy, John A. (2017) Electron transfer and hydride transfer pathways in the Stoltz-Grubbs reducing system (KOtBu-Et3SiH). Angewandte Chemie International Edition, 56 (44). 13747–13751. ISSN 1521-3773 (https://doi.org/10.1002/anie.201707914)

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Abstract

Recent studies by Stoltz, Grubbs et al. have shown that triethylsilane and potassium tert-butoxide react to form a highly attractive and versatile system that shows (reversible) silylation of arenes and heteroarenes as well as reductive cleavage of C-O bonds in aryl ethers and C-S bonds in aryl thioethers. Their extensive mechanistic studies indicate a complex network of reactions with a number of possible intermediates and mechanisms, but their reactions likely feature silyl radicals undergoing addition reactions and SH2 reactions. This paper focuses on the same system, but through computational and experimental studies, reports complementary facets of its chemistry based on (a) single electron transfer (SET), and (b) hydride delivery reactions to arenes.

ORCID iDs

Smith, Andrew J. ORCID logoORCID: https://orcid.org/0000-0001-7848-076X, Young, Allan ORCID logoORCID: https://orcid.org/0000-0002-1525-4703, Rohrbach, Simon, O'Connor, Erin F., Allison, Mark ORCID logoORCID: https://orcid.org/0000-0001-5597-7175, Wang, Hong-Shuang, Poole, Darren L., Tuttle, Tell and Murphy, John A.;
  • Item type:Article
    ID code:62101
    Dates:
    Date
    Event
    23 October 2017
    Published
    11 September 2017
    Published Online
    8 September 2017
    Accepted
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:20 Oct 2017 15:24
    Last modified:11 Nov 2024 11:47
    URI:https://strathprints.strath.ac.uk/id/eprint/62101
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