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Benzylic C−H Functionalisation by [Et 3 SiH+KO t Bu] leads to Radical Rearrangements in o‐ tolyl Aryl Ethers, Amines and Sulfides
Author(s) -
Arokianathar Jude N.,
Kolodziejczak Krystian,
Bugden Frances E.,
Clark Kenneth F.,
Tuttle Tell,
Murphy John A.
Publication year - 2020
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.202000356
Subject(s) - chemistry , radical , hydrogen atom abstraction , aryl , medicinal chemistry , alkyl , reactive intermediate , stereochemistry , photochemistry , organic chemistry , catalysis
Abstract Reaction of Et 3 SiH+KO t Bu 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.