New Insights in Frustrated Lewis Pair Chemistry with Azides

Devin H.A. Boom; Andrew R. Jupp; Martin Nieger; Andreas W. Ehlers; J. Chris Slootweg

doi:10.1002/chem.201902710

New Insights in Frustrated Lewis Pair Chemistry with Azides

Devin H.A. Boom, Andrew R. Jupp, Martin Nieger, Andreas W. Ehlers, J. Chris Slootweg^*

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

Abstract

The geminal frustrated Lewis pair (FLP) tBu₂PCH₂BPh₂ (1) reacts with phenyl-, mesityl-, and tert-butyl azide affording, respectively, six, five, and four-membered rings as isolable products. DFT calculations revealed that the formation of all products proceeds via the six-membered ring structure, which is thermally stable with an N-phenyl group, but rearranges when sterically more encumbered Mes−N₃ and tBu−N₃ are used. The reaction of 1 with Me₃Si−N₃ is believed to follow the same course, yet subsequent N₂ elimination occurs to afford a four-membered heterocycle (5), which can be considered as a formal FLP-trimethylsilylnitrene adduct. Compound 5 reacts with hydrochloric acid or tetramethylammonium fluoride and showed frustrated Lewis pair reactivity towards phenylisocyanate.

Original language	English
Pages (from-to)	13299-13308
Number of pages	10
Journal	Chemistry - A European Journal
Volume	25
Issue number	58
DOIs	https://doi.org/10.1002/chem.201902710
Publication status	Published - 17 Oct 2019
Externally published	Yes

Keywords

azides
density functional calculations
frustrated Lewis pairs
heterocycles
isocyanates

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10.1002/chem.201902710

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title = "New Insights in Frustrated Lewis Pair Chemistry with Azides",

abstract = "The geminal frustrated Lewis pair (FLP) tBu2PCH2BPh2 (1) reacts with phenyl-, mesityl-, and tert-butyl azide affording, respectively, six, five, and four-membered rings as isolable products. DFT calculations revealed that the formation of all products proceeds via the six-membered ring structure, which is thermally stable with an N-phenyl group, but rearranges when sterically more encumbered Mes−N3 and tBu−N3 are used. The reaction of 1 with Me3Si−N3 is believed to follow the same course, yet subsequent N2 elimination occurs to afford a four-membered heterocycle (5), which can be considered as a formal FLP-trimethylsilylnitrene adduct. Compound 5 reacts with hydrochloric acid or tetramethylammonium fluoride and showed frustrated Lewis pair reactivity towards phenylisocyanate.",

keywords = "azides, density functional calculations, frustrated Lewis pairs, heterocycles, isocyanates",

author = "Boom, {Devin H.A.} and Jupp, {Andrew R.} and Martin Nieger and Ehlers, {Andreas W.} and Slootweg, {J. Chris}",

year = "2019",

month = oct,

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doi = "10.1002/chem.201902710",

language = "English",

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T1 - New Insights in Frustrated Lewis Pair Chemistry with Azides

AU - Boom, Devin H.A.

AU - Jupp, Andrew R.

AU - Nieger, Martin

AU - Ehlers, Andreas W.

AU - Slootweg, J. Chris

PY - 2019/10/17

Y1 - 2019/10/17

N2 - The geminal frustrated Lewis pair (FLP) tBu2PCH2BPh2 (1) reacts with phenyl-, mesityl-, and tert-butyl azide affording, respectively, six, five, and four-membered rings as isolable products. DFT calculations revealed that the formation of all products proceeds via the six-membered ring structure, which is thermally stable with an N-phenyl group, but rearranges when sterically more encumbered Mes−N3 and tBu−N3 are used. The reaction of 1 with Me3Si−N3 is believed to follow the same course, yet subsequent N2 elimination occurs to afford a four-membered heterocycle (5), which can be considered as a formal FLP-trimethylsilylnitrene adduct. Compound 5 reacts with hydrochloric acid or tetramethylammonium fluoride and showed frustrated Lewis pair reactivity towards phenylisocyanate.

AB - The geminal frustrated Lewis pair (FLP) tBu2PCH2BPh2 (1) reacts with phenyl-, mesityl-, and tert-butyl azide affording, respectively, six, five, and four-membered rings as isolable products. DFT calculations revealed that the formation of all products proceeds via the six-membered ring structure, which is thermally stable with an N-phenyl group, but rearranges when sterically more encumbered Mes−N3 and tBu−N3 are used. The reaction of 1 with Me3Si−N3 is believed to follow the same course, yet subsequent N2 elimination occurs to afford a four-membered heterocycle (5), which can be considered as a formal FLP-trimethylsilylnitrene adduct. Compound 5 reacts with hydrochloric acid or tetramethylammonium fluoride and showed frustrated Lewis pair reactivity towards phenylisocyanate.

KW - azides

KW - density functional calculations

KW - frustrated Lewis pairs

KW - heterocycles

KW - isocyanates

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JF - Chemistry: A European Journal

SN - 0947-6539

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ER -

New Insights in Frustrated Lewis Pair Chemistry with Azides

Abstract

Keywords

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