1,6-Conjugate Additions of Carbon Nucleophiles to 2-[(1E,3E)-4-Arylbuta-1,3-dien-1-yl]-4H-chromen-4-ones

Hélio M.T. Albuquerque, Clementina M.M. Santos, Mannix P. Balanay, José A.S. Cavaleiro, Artur M.S. Silva

Research output: Contribution to journalArticle

Abstract

The 1,6-conjugate addition of nitromethane to 2-[(1E,3E)-4-arylbuta-1,3-dien-1-yl]-4H-chromen-4-ones was accomplished and led mainly to the corresponding β-(nitromethyl)chromones. (E)-5′-(Nitromethyl)-3′-styryl-[1,1′-biphenyl]-2-ol and 3′-aryl-2′-nitro-5′-(nitromethyl)spiro[chromane-2,1′-cyclohexan]-4-one derivatives were also isolated as minor products from tandem processes, which result from the addition of a second molecule of nitromethane. The nucleophile scope was investigated with malononitrile, acetylacetone, ethyl cyanoacetate, and diethyl malonate, which gave the expected 1,6-addition products; in the last case, it was also possible to isolate a minor product formed through a 1,8-/1,6-addition sequence. Computational calculations provided a rationale for the experimental reactivity of carbon nucleophiles with 2-[(1E,3E)-4-arylbuta-1,3-dien-1-yl]-4H-chromen-4-ones. The further functionalization of some adducts allowed the preparation of new nitrogen-containing heterocyclic compounds, such as new styrylpyrrolidines and new pyrazole and bis(pyrazole) derivatives.

Original languageEnglish
Pages (from-to)5293-5305
Number of pages13
JournalEuropean Journal of Organic Chemistry
Volume2017
Issue number35
DOIs
Publication statusPublished - Sep 25 2017

Fingerprint

Nucleophiles
nucleophiles
Carbon
Chromones
Derivatives
Heterocyclic Compounds
nitromethane
carbon
Nitrogen
products
malononitrile
heterocyclic compounds
acetylacetone
Molecules
adducts
reactivity
nitrogen
preparation
pyrazole
molecules

Keywords

  • Conjugate addition
  • Density functional calculations
  • Nitrogen heterocycles
  • Oxygen heterocycles

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

1,6-Conjugate Additions of Carbon Nucleophiles to 2-[(1E,3E)-4-Arylbuta-1,3-dien-1-yl]-4H-chromen-4-ones. / Albuquerque, Hélio M.T.; Santos, Clementina M.M.; Balanay, Mannix P.; Cavaleiro, José A.S.; Silva, Artur M.S.

In: European Journal of Organic Chemistry, Vol. 2017, No. 35, 25.09.2017, p. 5293-5305.

Research output: Contribution to journalArticle

Albuquerque, Hélio M.T. ; Santos, Clementina M.M. ; Balanay, Mannix P. ; Cavaleiro, José A.S. ; Silva, Artur M.S. / 1,6-Conjugate Additions of Carbon Nucleophiles to 2-[(1E,3E)-4-Arylbuta-1,3-dien-1-yl]-4H-chromen-4-ones. In: European Journal of Organic Chemistry. 2017 ; Vol. 2017, No. 35. pp. 5293-5305.
@article{0dbbf2ae1e234f4193b3cb5b101b0928,
title = "1,6-Conjugate Additions of Carbon Nucleophiles to 2-[(1E,3E)-4-Arylbuta-1,3-dien-1-yl]-4H-chromen-4-ones",
abstract = "The 1,6-conjugate addition of nitromethane to 2-[(1E,3E)-4-arylbuta-1,3-dien-1-yl]-4H-chromen-4-ones was accomplished and led mainly to the corresponding β-(nitromethyl)chromones. (E)-5′-(Nitromethyl)-3′-styryl-[1,1′-biphenyl]-2-ol and 3′-aryl-2′-nitro-5′-(nitromethyl)spiro[chromane-2,1′-cyclohexan]-4-one derivatives were also isolated as minor products from tandem processes, which result from the addition of a second molecule of nitromethane. The nucleophile scope was investigated with malononitrile, acetylacetone, ethyl cyanoacetate, and diethyl malonate, which gave the expected 1,6-addition products; in the last case, it was also possible to isolate a minor product formed through a 1,8-/1,6-addition sequence. Computational calculations provided a rationale for the experimental reactivity of carbon nucleophiles with 2-[(1E,3E)-4-arylbuta-1,3-dien-1-yl]-4H-chromen-4-ones. The further functionalization of some adducts allowed the preparation of new nitrogen-containing heterocyclic compounds, such as new styrylpyrrolidines and new pyrazole and bis(pyrazole) derivatives.",
keywords = "Conjugate addition, Density functional calculations, Nitrogen heterocycles, Oxygen heterocycles",
author = "Albuquerque, {H{\'e}lio M.T.} and Santos, {Clementina M.M.} and Balanay, {Mannix P.} and Cavaleiro, {Jos{\'e} A.S.} and Silva, {Artur M.S.}",
year = "2017",
month = "9",
day = "25",
doi = "10.1002/ejoc.201700944",
language = "English",
volume = "2017",
pages = "5293--5305",
journal = "Annalen der Pharmacie",
issn = "0075-4617",
publisher = "Wiley-VCH Verlag",
number = "35",

}

TY - JOUR

T1 - 1,6-Conjugate Additions of Carbon Nucleophiles to 2-[(1E,3E)-4-Arylbuta-1,3-dien-1-yl]-4H-chromen-4-ones

AU - Albuquerque, Hélio M.T.

AU - Santos, Clementina M.M.

AU - Balanay, Mannix P.

AU - Cavaleiro, José A.S.

AU - Silva, Artur M.S.

PY - 2017/9/25

Y1 - 2017/9/25

N2 - The 1,6-conjugate addition of nitromethane to 2-[(1E,3E)-4-arylbuta-1,3-dien-1-yl]-4H-chromen-4-ones was accomplished and led mainly to the corresponding β-(nitromethyl)chromones. (E)-5′-(Nitromethyl)-3′-styryl-[1,1′-biphenyl]-2-ol and 3′-aryl-2′-nitro-5′-(nitromethyl)spiro[chromane-2,1′-cyclohexan]-4-one derivatives were also isolated as minor products from tandem processes, which result from the addition of a second molecule of nitromethane. The nucleophile scope was investigated with malononitrile, acetylacetone, ethyl cyanoacetate, and diethyl malonate, which gave the expected 1,6-addition products; in the last case, it was also possible to isolate a minor product formed through a 1,8-/1,6-addition sequence. Computational calculations provided a rationale for the experimental reactivity of carbon nucleophiles with 2-[(1E,3E)-4-arylbuta-1,3-dien-1-yl]-4H-chromen-4-ones. The further functionalization of some adducts allowed the preparation of new nitrogen-containing heterocyclic compounds, such as new styrylpyrrolidines and new pyrazole and bis(pyrazole) derivatives.

AB - The 1,6-conjugate addition of nitromethane to 2-[(1E,3E)-4-arylbuta-1,3-dien-1-yl]-4H-chromen-4-ones was accomplished and led mainly to the corresponding β-(nitromethyl)chromones. (E)-5′-(Nitromethyl)-3′-styryl-[1,1′-biphenyl]-2-ol and 3′-aryl-2′-nitro-5′-(nitromethyl)spiro[chromane-2,1′-cyclohexan]-4-one derivatives were also isolated as minor products from tandem processes, which result from the addition of a second molecule of nitromethane. The nucleophile scope was investigated with malononitrile, acetylacetone, ethyl cyanoacetate, and diethyl malonate, which gave the expected 1,6-addition products; in the last case, it was also possible to isolate a minor product formed through a 1,8-/1,6-addition sequence. Computational calculations provided a rationale for the experimental reactivity of carbon nucleophiles with 2-[(1E,3E)-4-arylbuta-1,3-dien-1-yl]-4H-chromen-4-ones. The further functionalization of some adducts allowed the preparation of new nitrogen-containing heterocyclic compounds, such as new styrylpyrrolidines and new pyrazole and bis(pyrazole) derivatives.

KW - Conjugate addition

KW - Density functional calculations

KW - Nitrogen heterocycles

KW - Oxygen heterocycles

UR - http://www.scopus.com/inward/record.url?scp=85029852555&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85029852555&partnerID=8YFLogxK

U2 - 10.1002/ejoc.201700944

DO - 10.1002/ejoc.201700944

M3 - Article

VL - 2017

SP - 5293

EP - 5305

JO - Annalen der Pharmacie

JF - Annalen der Pharmacie

SN - 0075-4617

IS - 35

ER -