Synthesis of d-mannitol-based crown ethers and their application as catalyst in asymmetric phase transfer reactions

Tamás Nemcsok, Zsolt Rapi, G. Keglevich, A. Grün, P. Bakó

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

A few new d-mannitol-based monoaza-15-crown-5 type chiral lariat ethers and 18-crown-6 type macrocycles were synthesized. These crown compounds were used as phase transfer catalysts in asymmetric Michael addititons and in a Darzens condensation under mild conditions to afford the corresponding products in a few cases in good to excellent enantioselectivities. In the Michael addition of diethyl acetoxymalonate to trans-chalcone, in the addition of diethyl acetamidomalonate to ß-nitrostyrene, in the reaction of diethyl bromomalonate with benzylidene malononitriles, in the cyclopropanation reaction of diethyl bromomalonate and 2-benzylidene-1,3-indandione, and in the Darzens condensation of α-chloroacetophenone with benzaldehyde, maximum enantioselectivities of 39%, 65%, 99%, 56%, and 62%, respectively, were obtained in the presence of the d-mannitol-based macrocycles as the catalysts.

Original languageEnglish
Pages (from-to)407-419
Number of pages13
JournalChirality
Volume30
Issue number4
DOIs
Publication statusPublished - Apr 1 2018

Fingerprint

Crown Ethers
Crown ethers
Enantioselectivity
Mannitol
Crown Compounds
Condensation
omega-Chloroacetophenone
Chalcone
Catalysts
Ethers
1,3-indandione
dicyanmethane
15-crown-5
benzaldehyde
18-crown-6

Keywords

  • asymmetric Michael addition
  • Darzens condensation
  • phase transfer catalysis
  • sugar-based crown ethers

ASJC Scopus subject areas

  • Analytical Chemistry
  • Catalysis
  • Pharmacology
  • Drug Discovery
  • Spectroscopy
  • Organic Chemistry

Cite this

Synthesis of d-mannitol-based crown ethers and their application as catalyst in asymmetric phase transfer reactions. / Nemcsok, Tamás; Rapi, Zsolt; Keglevich, G.; Grün, A.; Bakó, P.

In: Chirality, Vol. 30, No. 4, 01.04.2018, p. 407-419.

Research output: Contribution to journalArticle

@article{e3cebc1342264c06961adb0c2236a267,
title = "Synthesis of d-mannitol-based crown ethers and their application as catalyst in asymmetric phase transfer reactions",
abstract = "A few new d-mannitol-based monoaza-15-crown-5 type chiral lariat ethers and 18-crown-6 type macrocycles were synthesized. These crown compounds were used as phase transfer catalysts in asymmetric Michael addititons and in a Darzens condensation under mild conditions to afford the corresponding products in a few cases in good to excellent enantioselectivities. In the Michael addition of diethyl acetoxymalonate to trans-chalcone, in the addition of diethyl acetamidomalonate to {\ss}-nitrostyrene, in the reaction of diethyl bromomalonate with benzylidene malononitriles, in the cyclopropanation reaction of diethyl bromomalonate and 2-benzylidene-1,3-indandione, and in the Darzens condensation of α-chloroacetophenone with benzaldehyde, maximum enantioselectivities of 39{\%}, 65{\%}, 99{\%}, 56{\%}, and 62{\%}, respectively, were obtained in the presence of the d-mannitol-based macrocycles as the catalysts.",
keywords = "asymmetric Michael addition, Darzens condensation, phase transfer catalysis, sugar-based crown ethers",
author = "Tam{\'a}s Nemcsok and Zsolt Rapi and G. Keglevich and A. Gr{\"u}n and P. Bak{\'o}",
year = "2018",
month = "4",
day = "1",
doi = "10.1002/chir.22800",
language = "English",
volume = "30",
pages = "407--419",
journal = "Chirality",
issn = "0899-0042",
publisher = "Wiley-Liss Inc.",
number = "4",

}

TY - JOUR

T1 - Synthesis of d-mannitol-based crown ethers and their application as catalyst in asymmetric phase transfer reactions

AU - Nemcsok, Tamás

AU - Rapi, Zsolt

AU - Keglevich, G.

AU - Grün, A.

AU - Bakó, P.

PY - 2018/4/1

Y1 - 2018/4/1

N2 - A few new d-mannitol-based monoaza-15-crown-5 type chiral lariat ethers and 18-crown-6 type macrocycles were synthesized. These crown compounds were used as phase transfer catalysts in asymmetric Michael addititons and in a Darzens condensation under mild conditions to afford the corresponding products in a few cases in good to excellent enantioselectivities. In the Michael addition of diethyl acetoxymalonate to trans-chalcone, in the addition of diethyl acetamidomalonate to ß-nitrostyrene, in the reaction of diethyl bromomalonate with benzylidene malononitriles, in the cyclopropanation reaction of diethyl bromomalonate and 2-benzylidene-1,3-indandione, and in the Darzens condensation of α-chloroacetophenone with benzaldehyde, maximum enantioselectivities of 39%, 65%, 99%, 56%, and 62%, respectively, were obtained in the presence of the d-mannitol-based macrocycles as the catalysts.

AB - A few new d-mannitol-based monoaza-15-crown-5 type chiral lariat ethers and 18-crown-6 type macrocycles were synthesized. These crown compounds were used as phase transfer catalysts in asymmetric Michael addititons and in a Darzens condensation under mild conditions to afford the corresponding products in a few cases in good to excellent enantioselectivities. In the Michael addition of diethyl acetoxymalonate to trans-chalcone, in the addition of diethyl acetamidomalonate to ß-nitrostyrene, in the reaction of diethyl bromomalonate with benzylidene malononitriles, in the cyclopropanation reaction of diethyl bromomalonate and 2-benzylidene-1,3-indandione, and in the Darzens condensation of α-chloroacetophenone with benzaldehyde, maximum enantioselectivities of 39%, 65%, 99%, 56%, and 62%, respectively, were obtained in the presence of the d-mannitol-based macrocycles as the catalysts.

KW - asymmetric Michael addition

KW - Darzens condensation

KW - phase transfer catalysis

KW - sugar-based crown ethers

UR - http://www.scopus.com/inward/record.url?scp=85039164299&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85039164299&partnerID=8YFLogxK

U2 - 10.1002/chir.22800

DO - 10.1002/chir.22800

M3 - Article

AN - SCOPUS:85039164299

VL - 30

SP - 407

EP - 419

JO - Chirality

JF - Chirality

SN - 0899-0042

IS - 4

ER -