Kinetic control wins out over thermodynamic control in Friedel-Crafts acyl rearrangements

Tahani Mala'bi; Sergey Pogodin; Israel Agranat

doi:10.1016/j.tetlet.2011.02.026

Kinetic control wins out over thermodynamic control in Friedel-Crafts acyl rearrangements

Tahani Mala'bi
, Sergey Pogodin
, Israel Agranat^*

^*Corresponding author for this work

Institute of Chemistry

Research output: Contribution to journal › Article › peer-review

8 Scopus citations

Abstract

1,5-, 1,8- and 9,10-diacetylanthracenes undergo Friedel-Crafts acyl rearrangements in polyphosphoric acid at 130-150 °C to give 3-methylbenz[de]anthracen-1-one via the kinetically-controlled 1,9-diacetylanthracene. The rearrangement mechanism is supported by DFT calculations of diacetylanthracenes, their σ-complexes, O-protonates, and O,O-diprotonates. The importance of kinetic control versus thermodynamic control in Friedel-Crafts acyl rearrangements is highlighted. Certain features of reversibility are also suggested.

Original language	English
Pages (from-to)	1854-1857
Number of pages	4
Journal	Tetrahedron Letters
Volume	52
Issue number	16
DOIs	https://doi.org/10.1016/j.tetlet.2011.02.026
State	Published - 20 Apr 2011

Keywords

DFT calculations
Diacetylanthracenes
Polyphosphoric acid
Rearrangement mechanism
Reversibility

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10.1016/j.tetlet.2011.02.026

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title = "Kinetic control wins out over thermodynamic control in Friedel-Crafts acyl rearrangements",

abstract = "1,5-, 1,8- and 9,10-diacetylanthracenes undergo Friedel-Crafts acyl rearrangements in polyphosphoric acid at 130-150 °C to give 3-methylbenz[de]anthracen-1-one via the kinetically-controlled 1,9-diacetylanthracene. The rearrangement mechanism is supported by DFT calculations of diacetylanthracenes, their σ-complexes, O-protonates, and O,O-diprotonates. The importance of kinetic control versus thermodynamic control in Friedel-Crafts acyl rearrangements is highlighted. Certain features of reversibility are also suggested.",

keywords = "DFT calculations, Diacetylanthracenes, Polyphosphoric acid, Rearrangement mechanism, Reversibility",

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AU - Mala'bi, Tahani

AU - Pogodin, Sergey

AU - Agranat, Israel

PY - 2011/4/20

Y1 - 2011/4/20

N2 - 1,5-, 1,8- and 9,10-diacetylanthracenes undergo Friedel-Crafts acyl rearrangements in polyphosphoric acid at 130-150 °C to give 3-methylbenz[de]anthracen-1-one via the kinetically-controlled 1,9-diacetylanthracene. The rearrangement mechanism is supported by DFT calculations of diacetylanthracenes, their σ-complexes, O-protonates, and O,O-diprotonates. The importance of kinetic control versus thermodynamic control in Friedel-Crafts acyl rearrangements is highlighted. Certain features of reversibility are also suggested.

AB - 1,5-, 1,8- and 9,10-diacetylanthracenes undergo Friedel-Crafts acyl rearrangements in polyphosphoric acid at 130-150 °C to give 3-methylbenz[de]anthracen-1-one via the kinetically-controlled 1,9-diacetylanthracene. The rearrangement mechanism is supported by DFT calculations of diacetylanthracenes, their σ-complexes, O-protonates, and O,O-diprotonates. The importance of kinetic control versus thermodynamic control in Friedel-Crafts acyl rearrangements is highlighted. Certain features of reversibility are also suggested.

KW - DFT calculations

KW - Diacetylanthracenes

KW - Polyphosphoric acid

KW - Rearrangement mechanism

KW - Reversibility

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AN - SCOPUS:79952735979

SN - 0040-4039

VL - 52

SP - 1854

EP - 1857

JO - Tetrahedron Letters

JF - Tetrahedron Letters

IS - 16

ER -

Kinetic control wins out over thermodynamic control in Friedel-Crafts acyl rearrangements

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Keywords

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