4 Citations (Scopus)

Abstract

An effective strategy was developed for the synthesis of new 2,2′-bipyridine ligands, symmetrical and unsymmetrical 6,6′-binicotinates, and 2,2′-bipyridine-5-carboxylates, from 4-propargylisoxazoles. The synthesis of symmetrical 2,2′-disubstituted 6,6′-binicotinates was achieved using the Eglinton reaction of 5-methoxy-4-(prop-2-yn-1-yl)isoxazoles with Cu(OAc) 2 , followed by Fe(NTf 2 ) 2 /Au(NTf 2 )tBuXPhos-catalyzed isomerization of the so-formed mixture of isoxazole/azirine-substituted biacetylenic intermediates. Unsymmetrical 2,2′-disubstituted 6,6′-binicotinates were prepared via a copper-free Sonogashira coupling of 5-methoxy-4-(prop-2-yn-1-yl)isoxazoles with 6-bromonicotinates to give methyl 6-(3-(5-methoxyisoxazol-4-yl)prop-1-ynyl)pyridine-3-carboxylates, followed by a transformation of the propargylisoxazole moiety of the adduct into the pyridine fragment under Fe(II)/Au(I) relay catalysis conditions. 6-(Pyrid-2-yl)nicotinates were synthesized by a Stille-type coupling of 2-(tributylstannyl)pyridine with 6-bromonicotinates. Several cyclopalladated complexes of a new series of 6,6′-binicotinates and 2,2′-bipyridine-5-carboxylates and the homoleptic Cu(I) complex were synthesized in high yields.

Original languageEnglish
Pages (from-to)3524-3536
Number of pages13
JournalJournal of Organic Chemistry
Volume84
Issue number6
DOIs
Publication statusPublished - 15 Mar 2019

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Isoxazoles
Coordination Complexes
Ligands
Isomerization
Catalysis
Copper
pyridine

Scopus subject areas

  • Organic Chemistry

Cite this

@article{e3011c23a4084b0cbf1627bb95776c78,
title = "Isoxazole Strategy for the Synthesis of 2,2′-Bipyridine Ligands: Symmetrical and Unsymmetrical 6,6′-Binicotinates, 2,2′-Bipyridine-5-carboxylates, and Their Metal Complexes",
abstract = "An effective strategy was developed for the synthesis of new 2,2′-bipyridine ligands, symmetrical and unsymmetrical 6,6′-binicotinates, and 2,2′-bipyridine-5-carboxylates, from 4-propargylisoxazoles. The synthesis of symmetrical 2,2′-disubstituted 6,6′-binicotinates was achieved using the Eglinton reaction of 5-methoxy-4-(prop-2-yn-1-yl)isoxazoles with Cu(OAc) 2 , followed by Fe(NTf 2 ) 2 /Au(NTf 2 )tBuXPhos-catalyzed isomerization of the so-formed mixture of isoxazole/azirine-substituted biacetylenic intermediates. Unsymmetrical 2,2′-disubstituted 6,6′-binicotinates were prepared via a copper-free Sonogashira coupling of 5-methoxy-4-(prop-2-yn-1-yl)isoxazoles with 6-bromonicotinates to give methyl 6-(3-(5-methoxyisoxazol-4-yl)prop-1-ynyl)pyridine-3-carboxylates, followed by a transformation of the propargylisoxazole moiety of the adduct into the pyridine fragment under Fe(II)/Au(I) relay catalysis conditions. 6-(Pyrid-2-yl)nicotinates were synthesized by a Stille-type coupling of 2-(tributylstannyl)pyridine with 6-bromonicotinates. Several cyclopalladated complexes of a new series of 6,6′-binicotinates and 2,2′-bipyridine-5-carboxylates and the homoleptic Cu(I) complex were synthesized in high yields.",
keywords = "ORGANIC FRAMEWORKS, FLUORESCENT-PROBE, ISOMERIZATION, BIPYRIDINE, MOLECULES",
author = "Galenko, {Ekaterina E.} and Novikov, {Mikhail S.} and Shakirova, {Firuza M.} and Shakirova, {Julia R.} and Kornyakov, {Ilya V.} and Bodunov, {Vladimir A.} and Khlebnikov, {Alexander F.}",
year = "2019",
month = "3",
day = "15",
doi = "10.1021/acs.joc.9b00115",
language = "English",
volume = "84",
pages = "3524--3536",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "6",

}

TY - JOUR

T1 - Isoxazole Strategy for the Synthesis of 2,2′-Bipyridine Ligands

T2 - Symmetrical and Unsymmetrical 6,6′-Binicotinates, 2,2′-Bipyridine-5-carboxylates, and Their Metal Complexes

AU - Galenko, Ekaterina E.

AU - Novikov, Mikhail S.

AU - Shakirova, Firuza M.

AU - Shakirova, Julia R.

AU - Kornyakov, Ilya V.

AU - Bodunov, Vladimir A.

AU - Khlebnikov, Alexander F.

PY - 2019/3/15

Y1 - 2019/3/15

N2 - An effective strategy was developed for the synthesis of new 2,2′-bipyridine ligands, symmetrical and unsymmetrical 6,6′-binicotinates, and 2,2′-bipyridine-5-carboxylates, from 4-propargylisoxazoles. The synthesis of symmetrical 2,2′-disubstituted 6,6′-binicotinates was achieved using the Eglinton reaction of 5-methoxy-4-(prop-2-yn-1-yl)isoxazoles with Cu(OAc) 2 , followed by Fe(NTf 2 ) 2 /Au(NTf 2 )tBuXPhos-catalyzed isomerization of the so-formed mixture of isoxazole/azirine-substituted biacetylenic intermediates. Unsymmetrical 2,2′-disubstituted 6,6′-binicotinates were prepared via a copper-free Sonogashira coupling of 5-methoxy-4-(prop-2-yn-1-yl)isoxazoles with 6-bromonicotinates to give methyl 6-(3-(5-methoxyisoxazol-4-yl)prop-1-ynyl)pyridine-3-carboxylates, followed by a transformation of the propargylisoxazole moiety of the adduct into the pyridine fragment under Fe(II)/Au(I) relay catalysis conditions. 6-(Pyrid-2-yl)nicotinates were synthesized by a Stille-type coupling of 2-(tributylstannyl)pyridine with 6-bromonicotinates. Several cyclopalladated complexes of a new series of 6,6′-binicotinates and 2,2′-bipyridine-5-carboxylates and the homoleptic Cu(I) complex were synthesized in high yields.

AB - An effective strategy was developed for the synthesis of new 2,2′-bipyridine ligands, symmetrical and unsymmetrical 6,6′-binicotinates, and 2,2′-bipyridine-5-carboxylates, from 4-propargylisoxazoles. The synthesis of symmetrical 2,2′-disubstituted 6,6′-binicotinates was achieved using the Eglinton reaction of 5-methoxy-4-(prop-2-yn-1-yl)isoxazoles with Cu(OAc) 2 , followed by Fe(NTf 2 ) 2 /Au(NTf 2 )tBuXPhos-catalyzed isomerization of the so-formed mixture of isoxazole/azirine-substituted biacetylenic intermediates. Unsymmetrical 2,2′-disubstituted 6,6′-binicotinates were prepared via a copper-free Sonogashira coupling of 5-methoxy-4-(prop-2-yn-1-yl)isoxazoles with 6-bromonicotinates to give methyl 6-(3-(5-methoxyisoxazol-4-yl)prop-1-ynyl)pyridine-3-carboxylates, followed by a transformation of the propargylisoxazole moiety of the adduct into the pyridine fragment under Fe(II)/Au(I) relay catalysis conditions. 6-(Pyrid-2-yl)nicotinates were synthesized by a Stille-type coupling of 2-(tributylstannyl)pyridine with 6-bromonicotinates. Several cyclopalladated complexes of a new series of 6,6′-binicotinates and 2,2′-bipyridine-5-carboxylates and the homoleptic Cu(I) complex were synthesized in high yields.

KW - ORGANIC FRAMEWORKS

KW - FLUORESCENT-PROBE

KW - ISOMERIZATION

KW - BIPYRIDINE

KW - MOLECULES

UR - http://www.scopus.com/inward/record.url?scp=85062856056&partnerID=8YFLogxK

U2 - 10.1021/acs.joc.9b00115

DO - 10.1021/acs.joc.9b00115

M3 - Article

C2 - 30810032

AN - SCOPUS:85062856056

VL - 84

SP - 3524

EP - 3536

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 6

ER -