Transition Metal-Catalyzed Synthesis of 3-Coumaranone-Containing NH-Aziridines from 2H-Azirines: Nickel(II) versus Gold(I)

Pavel A. Sakharov, Nikolai V. Rostovskii, Alexander F. Khlebnikov, Olesya V. Khoroshilova, Mikhail S. Novikov

Research output

Abstract

A catalytic nucleophilic addition reaction of 3-hydroxybenzofuran-2-carboxylic acid derivatives to 2H-azirines for the high-yield synthesis of NH-aziridines with a 3-coumaranone substituent has been developed. The Ph 3 PAuNTf 2 -catalyzed reaction is diastereoselective to give predominantly (RS,SR)-isomer of aziridine in good yield. The Ni(hfacac) 2 -catalyzed reaction affords aziridines in up to 98% yield and low or moderate diastereoselectivity, which in some cases is opposite to that observed for the gold(I)-catalyzed reaction. The Ph 3 PAuNTf 2 works well for sterically hindered azirines as well as benzofurans bearing electron-withdrawing groups, whereas Ni(hfacac) 2 is the catalyst of choice for the preparation of aziridines having diazoacetyl substituent. The latter compounds can serve as substrates for the synthesis of fused aziridines via Buchner ring expansion reaction. (Figure presented.).

Original languageEnglish
JournalAdvanced Synthesis and Catalysis
DOIs
Publication statusPublished - 1 Jan 2019

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Azirines
Aziridines
Nickel
Gold
Transition metals
Bearings (structural)
Addition reactions
Carboxylic acids
Isomers
Benzofurans
Derivatives
Catalysts
Electrons
Substrates
Carboxylic Acids
3-coumaranone

Scopus subject areas

  • Catalysis
  • Organic Chemistry

Cite this

@article{697ce08254364d7586e0518816fe219b,
title = "Transition Metal-Catalyzed Synthesis of 3-Coumaranone-Containing NH-Aziridines from 2H-Azirines: Nickel(II) versus Gold(I)",
abstract = "A catalytic nucleophilic addition reaction of 3-hydroxybenzofuran-2-carboxylic acid derivatives to 2H-azirines for the high-yield synthesis of NH-aziridines with a 3-coumaranone substituent has been developed. The Ph 3 PAuNTf 2 -catalyzed reaction is diastereoselective to give predominantly (RS,SR)-isomer of aziridine in good yield. The Ni(hfacac) 2 -catalyzed reaction affords aziridines in up to 98{\%} yield and low or moderate diastereoselectivity, which in some cases is opposite to that observed for the gold(I)-catalyzed reaction. The Ph 3 PAuNTf 2 works well for sterically hindered azirines as well as benzofurans bearing electron-withdrawing groups, whereas Ni(hfacac) 2 is the catalyst of choice for the preparation of aziridines having diazoacetyl substituent. The latter compounds can serve as substrates for the synthesis of fused aziridines via Buchner ring expansion reaction. (Figure presented.).",
keywords = "diazo compounds, gold, nickel, nitrogen heterocycles, oxygen heterocycles, Small ring systems",
author = "Sakharov, {Pavel A.} and Rostovskii, {Nikolai V.} and Khlebnikov, {Alexander F.} and Khoroshilova, {Olesya V.} and Novikov, {Mikhail S.}",
year = "2019",
month = "1",
day = "1",
doi = "10.1002/adsc.201900366",
language = "English",
journal = "Advanced Synthesis and Catalysis",
issn = "1615-4150",
publisher = "Wiley-Blackwell",

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TY - JOUR

T1 - Transition Metal-Catalyzed Synthesis of 3-Coumaranone-Containing NH-Aziridines from 2H-Azirines

T2 - Nickel(II) versus Gold(I)

AU - Sakharov, Pavel A.

AU - Rostovskii, Nikolai V.

AU - Khlebnikov, Alexander F.

AU - Khoroshilova, Olesya V.

AU - Novikov, Mikhail S.

PY - 2019/1/1

Y1 - 2019/1/1

N2 - A catalytic nucleophilic addition reaction of 3-hydroxybenzofuran-2-carboxylic acid derivatives to 2H-azirines for the high-yield synthesis of NH-aziridines with a 3-coumaranone substituent has been developed. The Ph 3 PAuNTf 2 -catalyzed reaction is diastereoselective to give predominantly (RS,SR)-isomer of aziridine in good yield. The Ni(hfacac) 2 -catalyzed reaction affords aziridines in up to 98% yield and low or moderate diastereoselectivity, which in some cases is opposite to that observed for the gold(I)-catalyzed reaction. The Ph 3 PAuNTf 2 works well for sterically hindered azirines as well as benzofurans bearing electron-withdrawing groups, whereas Ni(hfacac) 2 is the catalyst of choice for the preparation of aziridines having diazoacetyl substituent. The latter compounds can serve as substrates for the synthesis of fused aziridines via Buchner ring expansion reaction. (Figure presented.).

AB - A catalytic nucleophilic addition reaction of 3-hydroxybenzofuran-2-carboxylic acid derivatives to 2H-azirines for the high-yield synthesis of NH-aziridines with a 3-coumaranone substituent has been developed. The Ph 3 PAuNTf 2 -catalyzed reaction is diastereoselective to give predominantly (RS,SR)-isomer of aziridine in good yield. The Ni(hfacac) 2 -catalyzed reaction affords aziridines in up to 98% yield and low or moderate diastereoselectivity, which in some cases is opposite to that observed for the gold(I)-catalyzed reaction. The Ph 3 PAuNTf 2 works well for sterically hindered azirines as well as benzofurans bearing electron-withdrawing groups, whereas Ni(hfacac) 2 is the catalyst of choice for the preparation of aziridines having diazoacetyl substituent. The latter compounds can serve as substrates for the synthesis of fused aziridines via Buchner ring expansion reaction. (Figure presented.).

KW - diazo compounds

KW - gold

KW - nickel

KW - nitrogen heterocycles

KW - oxygen heterocycles

KW - Small ring systems

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U2 - 10.1002/adsc.201900366

DO - 10.1002/adsc.201900366

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