The Effect of Proximal Functionality on the Allylic Azide Equilibrium

Mary H. Packard; James H. Cox; Victoria P. Suding; Joseph J. Topczewski

doi:10.1002/ejoc.201700693

The Effect of Proximal Functionality on the Allylic Azide Equilibrium

Mary H. Packard, James H. Cox, Victoria P. Suding, Joseph J. Topczewski

Chemistry (Twin Cities)

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

11 Scopus citations

Abstract

This report describes an investigation into the effect that proximal functionality has on the allylic azide equilibrium. We report 16 allylic azides with varied functionality from three subclasses. We observe a correlation of % branched azide to the pKa of the OR group. We also observe that RN–H azides have a higher % branched azide relative the corresponding RN–Bn compound. These two effects combine to describe the observed equilibrium for the known compound hydroxy-crotyl azide. DFT calculations support several stereoelectronic effects that contribute to the relative energetics.

Original language	English (US)
Pages (from-to)	6365-6368
Number of pages	4
Journal	European Journal of Organic Chemistry
Volume	2017
Issue number	43
DOIs	https://doi.org/10.1002/ejoc.201700693
State	Published - Nov 24 2017

Bibliographical note

Funding Information:
We are grateful for helpful discussions with Grace Gast and Prof. Steve Kass. We gratefully acknowledge the University of Minnesota and the American Chemical Society's Petroleum Research Fund (PRF # 56505-DNI1) for financial support. The Minnesota Supercomputing Institute (MSI) at the University of Minnesota provided resources that contributed to the results reported within this paper.

Publisher Copyright:
© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

Amines
Azides
Click chemistry

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10.1002/ejoc.201700693

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abstract = "This report describes an investigation into the effect that proximal functionality has on the allylic azide equilibrium. We report 16 allylic azides with varied functionality from three subclasses. We observe a correlation of % branched azide to the pKa of the OR group. We also observe that RN–H azides have a higher % branched azide relative the corresponding RN–Bn compound. These two effects combine to describe the observed equilibrium for the known compound hydroxy-crotyl azide. DFT calculations support several stereoelectronic effects that contribute to the relative energetics.",

keywords = "Amines, Azides, Click chemistry",

author = "Packard, {Mary H.} and Cox, {James H.} and Suding, {Victoria P.} and Topczewski, {Joseph J.}",

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AU - Cox, James H.

AU - Suding, Victoria P.

AU - Topczewski, Joseph J.

N1 - Funding Information: We are grateful for helpful discussions with Grace Gast and Prof. Steve Kass. We gratefully acknowledge the University of Minnesota and the American Chemical Society's Petroleum Research Fund (PRF # 56505-DNI1) for financial support. The Minnesota Supercomputing Institute (MSI) at the University of Minnesota provided resources that contributed to the results reported within this paper. Publisher Copyright: © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2017/11/24

Y1 - 2017/11/24

N2 - This report describes an investigation into the effect that proximal functionality has on the allylic azide equilibrium. We report 16 allylic azides with varied functionality from three subclasses. We observe a correlation of % branched azide to the pKa of the OR group. We also observe that RN–H azides have a higher % branched azide relative the corresponding RN–Bn compound. These two effects combine to describe the observed equilibrium for the known compound hydroxy-crotyl azide. DFT calculations support several stereoelectronic effects that contribute to the relative energetics.

AB - This report describes an investigation into the effect that proximal functionality has on the allylic azide equilibrium. We report 16 allylic azides with varied functionality from three subclasses. We observe a correlation of % branched azide to the pKa of the OR group. We also observe that RN–H azides have a higher % branched azide relative the corresponding RN–Bn compound. These two effects combine to describe the observed equilibrium for the known compound hydroxy-crotyl azide. DFT calculations support several stereoelectronic effects that contribute to the relative energetics.

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KW - Azides

KW - Click chemistry

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SN - 1434-193X

IS - 43

ER -

The Effect of Proximal Functionality on the Allylic Azide Equilibrium

Abstract

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Keywords

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