Oxygen Atom Transfer as Key to Reverse Regioselectivity in the Gold(I)-Catalyzed Generation of Aminooxazoles from Ynamides

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Oxygen Atom Transfer as Key to Reverse Regioselectivity in the Gold(I)-Catalyzed Generation of Aminooxazoles from Ynamides. / Zimin, Dmitry P.; Dar'In, Dmitry V.; Kukushkin, Vadim Yu ; Dubovtsev, Alexey Yu.

In: Journal of Organic Chemistry, Vol. 86, No. 2, 15.01.2021, p. 1748-1757.

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

BibTeX

@article{d22555f339ee460aab95e0f71e23640a,

title = "Oxygen Atom Transfer as Key to Reverse Regioselectivity in the Gold(I)-Catalyzed Generation of Aminooxazoles from Ynamides",

abstract = "We report on gold(I)-catalyzed oxidative annulation involving ynamides, nitriles, and 2,3-dichloropyridine N-oxide. The application of 2,3-dichloropyridine N-oxide as an oxygen atom transfer reagent reverses the regioselectivity to give 5-amino-1,3-oxazoles, in comparison with the previously reported syntheses of aminooxazoles based on gold-catalyzed nitrene transfers to ynamides to furnish 4-amino-1,3-oxazoles. The developed oxygen atom transfer approach allows the generation of 1,3-oxazoles containing a variety of sulfonyl-protected alkylamino groups in the fifth position of the oxazole ring (29 examples; up to 88% yields). In addition, the use of N-substituted nitriles, namely cyanamides, leads to the facile generation of difficult-to-obtain 2,5-diaminooxazoles. The process is feasible for wide ranges of ynamides or nitriles, and it can be conducted in gram scale. ",

author = "Zimin, {Dmitry P.} and Dar'In, {Dmitry V.} and Kukushkin, {Vadim Yu} and Dubovtsev, {Alexey Yu}",

note = "Funding Information: A.Yu.D. thanks the Russian Science Foundation for support of these studies (grant 20-73-10022). We are much obliged to the Center for Magnetic Resonance, Center for Chemical Analysis and Material Research, Center for X-ray Diffraction Studies (all belonging to Saint Petersburg State University) for physicochemical measurements. V.Y.K. thanks South Ural State University (Act 211 Government of the Russian Federation, contract 02.A03.21.0011) for putting facilities at the author{\textquoteright}s disposal. Publisher Copyright: {\textcopyright} 2021 American Chemical Society. All rights reserved. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.",

year = "2021",

month = jan,

day = "15",

doi = "10.1021/acs.joc.0c02584",

language = "English",

volume = "86",

pages = "1748--1757",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society",

number = "2",

}

RIS

TY - JOUR

T1 - Oxygen Atom Transfer as Key to Reverse Regioselectivity in the Gold(I)-Catalyzed Generation of Aminooxazoles from Ynamides

AU - Zimin, Dmitry P.

AU - Dar'In, Dmitry V.

AU - Kukushkin, Vadim Yu

AU - Dubovtsev, Alexey Yu

N1 - Funding Information: A.Yu.D. thanks the Russian Science Foundation for support of these studies (grant 20-73-10022). We are much obliged to the Center for Magnetic Resonance, Center for Chemical Analysis and Material Research, Center for X-ray Diffraction Studies (all belonging to Saint Petersburg State University) for physicochemical measurements. V.Y.K. thanks South Ural State University (Act 211 Government of the Russian Federation, contract 02.A03.21.0011) for putting facilities at the author’s disposal. Publisher Copyright: © 2021 American Chemical Society. All rights reserved. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/1/15

Y1 - 2021/1/15

N2 - We report on gold(I)-catalyzed oxidative annulation involving ynamides, nitriles, and 2,3-dichloropyridine N-oxide. The application of 2,3-dichloropyridine N-oxide as an oxygen atom transfer reagent reverses the regioselectivity to give 5-amino-1,3-oxazoles, in comparison with the previously reported syntheses of aminooxazoles based on gold-catalyzed nitrene transfers to ynamides to furnish 4-amino-1,3-oxazoles. The developed oxygen atom transfer approach allows the generation of 1,3-oxazoles containing a variety of sulfonyl-protected alkylamino groups in the fifth position of the oxazole ring (29 examples; up to 88% yields). In addition, the use of N-substituted nitriles, namely cyanamides, leads to the facile generation of difficult-to-obtain 2,5-diaminooxazoles. The process is feasible for wide ranges of ynamides or nitriles, and it can be conducted in gram scale.

AB - We report on gold(I)-catalyzed oxidative annulation involving ynamides, nitriles, and 2,3-dichloropyridine N-oxide. The application of 2,3-dichloropyridine N-oxide as an oxygen atom transfer reagent reverses the regioselectivity to give 5-amino-1,3-oxazoles, in comparison with the previously reported syntheses of aminooxazoles based on gold-catalyzed nitrene transfers to ynamides to furnish 4-amino-1,3-oxazoles. The developed oxygen atom transfer approach allows the generation of 1,3-oxazoles containing a variety of sulfonyl-protected alkylamino groups in the fifth position of the oxazole ring (29 examples; up to 88% yields). In addition, the use of N-substituted nitriles, namely cyanamides, leads to the facile generation of difficult-to-obtain 2,5-diaminooxazoles. The process is feasible for wide ranges of ynamides or nitriles, and it can be conducted in gram scale.

UR - http://www.scopus.com/inward/record.url?scp=85099095862&partnerID=8YFLogxK

U2 - 10.1021/acs.joc.0c02584

DO - 10.1021/acs.joc.0c02584

M3 - Article

AN - SCOPUS:85099095862

VL - 86

SP - 1748

EP - 1757

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 2

ER -

ID: 75381319