Synchronized aromaticity as an enthalpic driving force for the aromatic cope rearrangement

David J. Babinski; Xiaoguang Bao; Marie El Arba; Bo Chen; David A. Hrovat; Weston Thatcher Borden; Doug E. Frantz

doi:10.1021/ja307213m

Synchronized aromaticity as an enthalpic driving force for the aromatic cope rearrangement

David J. Babinski, Xiaoguang Bao, Marie El Arba, Bo Chen, David A. Hrovat, Weston Thatcher Borden, Doug E. Frantz

Chemistry

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

29 Scopus citations

Abstract

We report herein experimental and theoretical evidence for an aromatic Cope rearrangement. Along with several successful examples, our data include the first isolation and full characterization of the putative intermediate that is formed immediately after the initial [3,3] sigmatropic rearrangement. Calculations at the B3LYP/6-31G(d) level of theory predict reaction energy barriers in the range 22-23 kcal/mol for the [3,3]-rearrangement consistent with the exceptionally mild reaction conditions for these reactions. The experimental and computational results support a significant enthalpic contribution of the concomitant pyrazole ring formation that serves as both a kinetic and thermodynamic driving force for the aromatic Cope rearrangement.

Original language	English (US)
Pages (from-to)	16139-16142
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	134
Issue number	39
DOIs	https://doi.org/10.1021/ja307213m
State	Published - Oct 3 2012

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "Synchronized aromaticity as an enthalpic driving force for the aromatic cope rearrangement",

abstract = "We report herein experimental and theoretical evidence for an aromatic Cope rearrangement. Along with several successful examples, our data include the first isolation and full characterization of the putative intermediate that is formed immediately after the initial [3,3] sigmatropic rearrangement. Calculations at the B3LYP/6-31G(d) level of theory predict reaction energy barriers in the range 22-23 kcal/mol for the [3,3]-rearrangement consistent with the exceptionally mild reaction conditions for these reactions. The experimental and computational results support a significant enthalpic contribution of the concomitant pyrazole ring formation that serves as both a kinetic and thermodynamic driving force for the aromatic Cope rearrangement.",

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T1 - Synchronized aromaticity as an enthalpic driving force for the aromatic cope rearrangement

AU - Babinski, David J.

AU - Bao, Xiaoguang

AU - El Arba, Marie

AU - Chen, Bo

AU - Hrovat, David A.

AU - Borden, Weston Thatcher

AU - Frantz, Doug E.

PY - 2012/10/3

Y1 - 2012/10/3

N2 - We report herein experimental and theoretical evidence for an aromatic Cope rearrangement. Along with several successful examples, our data include the first isolation and full characterization of the putative intermediate that is formed immediately after the initial [3,3] sigmatropic rearrangement. Calculations at the B3LYP/6-31G(d) level of theory predict reaction energy barriers in the range 22-23 kcal/mol for the [3,3]-rearrangement consistent with the exceptionally mild reaction conditions for these reactions. The experimental and computational results support a significant enthalpic contribution of the concomitant pyrazole ring formation that serves as both a kinetic and thermodynamic driving force for the aromatic Cope rearrangement.

AB - We report herein experimental and theoretical evidence for an aromatic Cope rearrangement. Along with several successful examples, our data include the first isolation and full characterization of the putative intermediate that is formed immediately after the initial [3,3] sigmatropic rearrangement. Calculations at the B3LYP/6-31G(d) level of theory predict reaction energy barriers in the range 22-23 kcal/mol for the [3,3]-rearrangement consistent with the exceptionally mild reaction conditions for these reactions. The experimental and computational results support a significant enthalpic contribution of the concomitant pyrazole ring formation that serves as both a kinetic and thermodynamic driving force for the aromatic Cope rearrangement.

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Synchronized aromaticity as an enthalpic driving force for the aromatic cope rearrangement

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