Pseudocyclic Arylbenziodoxaboroles: Efficient Benzyne Precursors Triggered by Water at Room Temperature

Akira Yoshimura; Jonathan M. Fuchs; Kyle R. Middleton; Andrey V. Maskaev; Gregory T. Rohde; Akio Saito; Pavel S. Postnikov; Mekhman S. Yusubov; Victor N. Nemykin; Viktor V. Zhdankin

doi:10.1002/chem.201704393

Pseudocyclic Arylbenziodoxaboroles: Efficient Benzyne Precursors Triggered by Water at Room Temperature

Akira Yoshimura, Jonathan M. Fuchs, Kyle R. Middleton, Andrey V. Maskaev, Gregory T. Rohde, Akio Saito, Pavel S. Postnikov, Mekhman S. Yusubov, Victor N. Nemykin, Viktor V. Zhdankin

Chemistry & Biochemistry

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

37 Scopus citations

Abstract

New organohypervalent iodine compounds, arylbenziodoxaborole triflates, were prepared from 1-acetoxybenziodoxaboroles and arenes by treatment with trifluoromethanesulfonic acid under mild conditions. Single crystal X-ray crystallography of these compounds revealed a pseudocyclic structure with a short intramolecular interaction of 2.698 to 2.717 Å between oxygen and iodine in the benziodoxaborole ring. These new pseudocyclic aryliodonium salts readily generate aryne intermediates upon treatment with water at room temperature. The generated aryne intermediates react with various substrates to give the corresponding aryne adducts in moderate to good yields. Furthermore, the new benzyne precursors can also work as arylating reagents towards aromatic rings. The aryne intermediates generated from arylbenziodoxaborole triflates selectively react with tert-butyl phenol forming products of ortho arylation in moderate yields.

Original language	English (US)
Pages (from-to)	16738-16742
Number of pages	5
Journal	Chemistry - A European Journal
Volume	23
Issue number	66
DOIs	https://doi.org/10.1002/chem.201704393
State	Published - Nov 27 2017

Bibliographical note

Funding Information:
This work was supported by research grants from the National Science Foundation (CHE-1262479), the Russian Science Foun- dation (RSF-16-13-10081), and Tomsk Polytechnic University (VIU-316/2017). A.S. is also thankful to JSPS Grants-in-Aid for Scientific Research (C) (Grant No 15K07852).

Funding Information:
This work was supported by research grants from the National Science Foundation (CHE-1262479), the Russian Science Foundation (RSF-16-13-10081), and Tomsk Polytechnic University (VIU-316/2017). A.S. is also thankful to JSPS Grants-in-Aid for Scientific Research (C) (Grant No 15K07852).

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

Keywords

arynes
benzyne
hypervalent iodine
iodine
iodonium

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title = "Pseudocyclic Arylbenziodoxaboroles: Efficient Benzyne Precursors Triggered by Water at Room Temperature",

abstract = "New organohypervalent iodine compounds, arylbenziodoxaborole triflates, were prepared from 1-acetoxybenziodoxaboroles and arenes by treatment with trifluoromethanesulfonic acid under mild conditions. Single crystal X-ray crystallography of these compounds revealed a pseudocyclic structure with a short intramolecular interaction of 2.698 to 2.717 {\AA} between oxygen and iodine in the benziodoxaborole ring. These new pseudocyclic aryliodonium salts readily generate aryne intermediates upon treatment with water at room temperature. The generated aryne intermediates react with various substrates to give the corresponding aryne adducts in moderate to good yields. Furthermore, the new benzyne precursors can also work as arylating reagents towards aromatic rings. The aryne intermediates generated from arylbenziodoxaborole triflates selectively react with tert-butyl phenol forming products of ortho arylation in moderate yields.",

keywords = "arynes, benzyne, hypervalent iodine, iodine, iodonium",

author = "Akira Yoshimura and Fuchs, {Jonathan M.} and Middleton, {Kyle R.} and Maskaev, {Andrey V.} and Rohde, {Gregory T.} and Akio Saito and Postnikov, {Pavel S.} and Yusubov, {Mekhman S.} and Nemykin, {Victor N.} and Zhdankin, {Viktor V.}",

note = "Funding Information: This work was supported by research grants from the National Science Foundation (CHE-1262479), the Russian Science Foun- dation (RSF-16-13-10081), and Tomsk Polytechnic University (VIU-316/2017). A.S. is also thankful to JSPS Grants-in-Aid for Scientific Research (C) (Grant No 15K07852). Funding Information: This work was supported by research grants from the National Science Foundation (CHE-1262479), the Russian Science Foundation (RSF-16-13-10081), and Tomsk Polytechnic University (VIU-316/2017). A.S. is also thankful to JSPS Grants-in-Aid for Scientific Research (C) (Grant No 15K07852). Publisher Copyright: {\textcopyright} 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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AU - Postnikov, Pavel S.

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AU - Nemykin, Victor N.

AU - Zhdankin, Viktor V.

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N2 - New organohypervalent iodine compounds, arylbenziodoxaborole triflates, were prepared from 1-acetoxybenziodoxaboroles and arenes by treatment with trifluoromethanesulfonic acid under mild conditions. Single crystal X-ray crystallography of these compounds revealed a pseudocyclic structure with a short intramolecular interaction of 2.698 to 2.717 Å between oxygen and iodine in the benziodoxaborole ring. These new pseudocyclic aryliodonium salts readily generate aryne intermediates upon treatment with water at room temperature. The generated aryne intermediates react with various substrates to give the corresponding aryne adducts in moderate to good yields. Furthermore, the new benzyne precursors can also work as arylating reagents towards aromatic rings. The aryne intermediates generated from arylbenziodoxaborole triflates selectively react with tert-butyl phenol forming products of ortho arylation in moderate yields.

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Pseudocyclic Arylbenziodoxaboroles: Efficient Benzyne Precursors Triggered by Water at Room Temperature

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