Benzylic C-H functionalisation by [Et3SiH + KOtBu] leads to radical rearrangements in o-tolylaryl ethers, amines
Arokianathar, Jude N. and Kolodziejczak, Krystian and Bugden, Frances E. and Clark, Kenneth F. and Tuttle, Tell and Murphy, John A. (2020) Benzylic C-H functionalisation by [Et3SiH + KOtBu] leads to radical rearrangements in o-tolylaryl ethers, amines. Advanced Synthesis and Catalysis, 362 (11). pp. 2260-2267. ISSN 1615-4150
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Abstract
Reaction of Et 3SiH+KO tBu with diaryl ethers, sulfides and amines that feature an ortho alkyl group leads to rearrangement products. The rearrangements arise from formation of benzyl radicals, likely formed through hydrogen atom abstraction by triethylsilyl radicals. The rearrangements involve cyclisation of the benzyl radical onto the partner arene, which, from computation, is the rate determining step. In the case of diaryl ethers, Truce-Smiles rearrangements arise from radical cyclisations to form 5-membered rings, but for diarylamines, cyclisations to form dihydroacridines are observed. (Figure presented.).
ORCID iDs
Arokianathar, Jude N.
ORCID: https://orcid.org/0000-0003-4770-2432, Kolodziejczak, Krystian, Bugden, Frances E., Clark, Kenneth F., Tuttle, Tell and Murphy, John A.;
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Item type: Article ID code: 72297 Dates: DateEvent26 May 2020Published14 April 2020Published Online14 April 2020AcceptedKeywords: radical, Truce-Smiles rearrangement, silane, KOtBu, Chemistry, Chemistry(all) Subjects: Science > Chemistry Department: Faculty of Science > Pure and Applied Chemistry Depositing user: Pure Administrator Date deposited: 07 May 2020 10:09 Last modified: 18 Nov 2021 02:16 URI: https://strathprints.strath.ac.uk/id/eprint/72297
CORE (COnnecting REpositories)
CORE (COnnecting REpositories)