Benzylic C-H functionalisation by [Et3SiH + KOtBu] leads to radical rearrangements in o-tolylaryl ethers, amines

Jude N. Arokianathar; Krystian Kolodziejczak; Frances E. Bugden; Kenneth F. Clark; Tell Tuttle; John A. Murphy

doi:10.1002/adsc.202000356

Benzylic C-H functionalisation by [Et₃SiH + KO^tBu] leads to radical rearrangements in o-tolylaryl ethers, amines

Jude N. Arokianathar, Krystian Kolodziejczak, Frances E. Bugden, Kenneth F. Clark, Tell Tuttle, John A. Murphy

Pure And Applied Chemistry

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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.).

Original language	English
Pages (from-to)	2260-2267
Number of pages	8
Journal	Advanced Synthesis and Catalysis
Volume	362
Issue number	11
Early online date	14 Apr 2020
DOIs	https://doi.org/10.1002/adsc.202000356
Publication status	Published - 26 May 2020

Keywords

radical
Truce-Smiles rearrangement
silane
KOtBu

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Arokianathar-etal-ASC-2020-Benzylic-C-H-functionalisationFinal published version, 3.95 MBLicence: CC BY 4.0

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Cite this

@article{6d8faeb35a8a4055b103f6b8a2f0d63d,

title = "Benzylic C-H functionalisation by [Et3SiH + KOtBu] leads to radical rearrangements in o-tolylaryl ethers, amines",

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.). ",

keywords = "radical, Truce-Smiles rearrangement, silane, KOtBu",

author = "Arokianathar, {Jude N.} and Krystian Kolodziejczak and Bugden, {Frances E.} and Clark, {Kenneth F.} and Tell Tuttle and Murphy, {John A.}",

year = "2020",

month = may,

day = "26",

doi = "10.1002/adsc.202000356",

language = "English",

volume = "362",

pages = "2260--2267",

journal = "Advanced Synthesis and Catalysis",

issn = "1615-4150",

number = "11",

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TY - JOUR

T1 - Benzylic C-H functionalisation by [Et3SiH + KOtBu] leads to radical rearrangements in o-tolylaryl ethers, amines

AU - Arokianathar, Jude N.

AU - Kolodziejczak, Krystian

AU - Bugden, Frances E.

AU - Clark, Kenneth F.

AU - Tuttle, Tell

AU - Murphy, John A.

PY - 2020/5/26

Y1 - 2020/5/26

N2 - 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.).

AB - 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.).

KW - radical

KW - Truce-Smiles rearrangement

KW - silane

KW - KOtBu

U2 - 10.1002/adsc.202000356

DO - 10.1002/adsc.202000356

M3 - Article

SN - 1615-4150

VL - 362

SP - 2260

EP - 2267

JO - Advanced Synthesis and Catalysis

JF - Advanced Synthesis and Catalysis

IS - 11

ER -

Benzylic C-H functionalisation by [Et3SiH + KOtBu] leads to radical rearrangements in o-tolylaryl ethers, amines

Abstract

Keywords

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Benzylic C-H functionalisation by [Et₃SiH + KO^tBu] leads to radical rearrangements in o-tolylaryl ethers, amines