Synthesis of Polysubstituted Meta-Halophenols by Anion-Accelerated 2π-Electrocyclic Ring-Opening

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Standard

Synthesis of Polysubstituted Meta-Halophenols by Anion-Accelerated 2π-Electrocyclic Ring-Opening. / Staudt, Markus; Sølling, Theis Ivan; Bunch, Lennart.

I: Chemistry - A European Journal, Bind 27, Nr. 42, 2021, s. 10941–10947.

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt

Harvard

Staudt, M, Sølling, TI & Bunch, L 2021, 'Synthesis of Polysubstituted Meta-Halophenols by Anion-Accelerated 2π-Electrocyclic Ring-Opening', Chemistry - A European Journal, bind 27, nr. 42, s. 10941–10947. https://doi.org/10.1002/chem.202100939

APA

Staudt, M., Sølling, T. I., & Bunch, L. (2021). Synthesis of Polysubstituted Meta-Halophenols by Anion-Accelerated 2π-Electrocyclic Ring-Opening. Chemistry - A European Journal, 27(42), 10941–10947. https://doi.org/10.1002/chem.202100939

Vancouver

Staudt M, Sølling TI, Bunch L. Synthesis of Polysubstituted Meta-Halophenols by Anion-Accelerated 2π-Electrocyclic Ring-Opening. Chemistry - A European Journal. 2021;27(42):10941–10947. https://doi.org/10.1002/chem.202100939

Author

Staudt, Markus ; Sølling, Theis Ivan ; Bunch, Lennart. / Synthesis of Polysubstituted Meta-Halophenols by Anion-Accelerated 2π-Electrocyclic Ring-Opening. I: Chemistry - A European Journal. 2021 ; Bind 27, Nr. 42. s. 10941–10947.

Bibtex

@article{045f62cae95a42fdacacd5f043e536b6,
title = "Synthesis of Polysubstituted Meta-Halophenols by Anion-Accelerated 2π-Electrocyclic Ring-Opening",
abstract = "Disrotatory – thermally allowed – 2π-electrocyclic ring-opening reactions require high temperatures to proceed. Herein, we report the first anion-accelerated 2π-electrocyclic ring opening of 6,6-dihalobicyclo[3.1.0]hexan-2-ones at low temperature to give the corresponding meta-halophenols in good to high yields (18 examples, 29–92 % yield, average: 65 %). Many of the phenols have unconventional substitution patterns and are reported here for the first time. Furthermore, the strength of the methodology was shown by the total synthesis of the densely functionalized phenolic natural product caramboxin (isolated as the lactam dehydrate). The reaction mechanism underlying the anion-acceleration was investigated in an ab initio study, which concluded that base-mediated proton abstraction anti to the concurrently departing endo-bromine was the initiating step in an overall concerted reaction mechanism leading directly to the meta-halophenol.",
author = "Markus Staudt and S{\o}lling, {Theis Ivan} and Lennart Bunch",
year = "2021",
doi = "10.1002/chem.202100939",
language = "English",
volume = "27",
pages = "10941–10947",
journal = "Chemistry: A European Journal",
issn = "0947-6539",
publisher = "Wiley - V C H Verlag GmbH & Co. KGaA",
number = "42",

}

RIS

TY - JOUR

T1 - Synthesis of Polysubstituted Meta-Halophenols by Anion-Accelerated 2π-Electrocyclic Ring-Opening

AU - Staudt, Markus

AU - Sølling, Theis Ivan

AU - Bunch, Lennart

PY - 2021

Y1 - 2021

N2 - Disrotatory – thermally allowed – 2π-electrocyclic ring-opening reactions require high temperatures to proceed. Herein, we report the first anion-accelerated 2π-electrocyclic ring opening of 6,6-dihalobicyclo[3.1.0]hexan-2-ones at low temperature to give the corresponding meta-halophenols in good to high yields (18 examples, 29–92 % yield, average: 65 %). Many of the phenols have unconventional substitution patterns and are reported here for the first time. Furthermore, the strength of the methodology was shown by the total synthesis of the densely functionalized phenolic natural product caramboxin (isolated as the lactam dehydrate). The reaction mechanism underlying the anion-acceleration was investigated in an ab initio study, which concluded that base-mediated proton abstraction anti to the concurrently departing endo-bromine was the initiating step in an overall concerted reaction mechanism leading directly to the meta-halophenol.

AB - Disrotatory – thermally allowed – 2π-electrocyclic ring-opening reactions require high temperatures to proceed. Herein, we report the first anion-accelerated 2π-electrocyclic ring opening of 6,6-dihalobicyclo[3.1.0]hexan-2-ones at low temperature to give the corresponding meta-halophenols in good to high yields (18 examples, 29–92 % yield, average: 65 %). Many of the phenols have unconventional substitution patterns and are reported here for the first time. Furthermore, the strength of the methodology was shown by the total synthesis of the densely functionalized phenolic natural product caramboxin (isolated as the lactam dehydrate). The reaction mechanism underlying the anion-acceleration was investigated in an ab initio study, which concluded that base-mediated proton abstraction anti to the concurrently departing endo-bromine was the initiating step in an overall concerted reaction mechanism leading directly to the meta-halophenol.

U2 - 10.1002/chem.202100939

DO - 10.1002/chem.202100939

M3 - Journal article

C2 - 34041800

VL - 27

SP - 10941

EP - 10947

JO - Chemistry: A European Journal

JF - Chemistry: A European Journal

SN - 0947-6539

IS - 42

ER -

ID: 269518180