Crown ether derived from D-glucose as an efficient phase-transfer catalyst for the enantioselective Michael addition of malonates to enones

Zsolt Rapi, A. Grün, Tamás Nemcsok, Dóra Hessz, M. Kállay, M. Kubinyi, G. Keglevich, P. Bakó

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Abstract

A monoaza-15-crown-5 lariat ether derived from D-glucose 1 has been applied as a chiral phase-transfer catalyst in the Michael addition of diethyl, dimethyl, diisopropyl and dibenzyl malonates to enones under mild conditions to afford the adducts with good to excellent enantioselectivities. In the reaction of diethyl malonate with substituted trans-chalcone, the adducts with in enantioselectivities up to 89% ee. Among the reactions of substituted diethyl malonates, those of diethyl acetoxymalonate gave the best results (96% ee). The effect of the substituents of the chalcone was also investigated in reactions with diethyl acetoxymalonate. Among the chalcones substituted on the β-aryl, the para-substituted compounds resulted in the highest enantioselectivities (88–97% ee). The substituents on the benzoyl aryl of chalcone caused a decrease in the enantioselectivity compared to the unsubstituted case. The adducts with furyl or thiophenyl substituents were formed with >99% ee. The glucose-based catalyst also proved to be effective in the cases of diisopropyl and dibenzyl acetoxymalonates (including ees up to 99% ee). The reactions of diethyl acetoxymalonate with cyclic enones gave the corresponding Michael adducts with enantioselectivities up to 83%. The absolute configuration of one of the new Michael adducts was determined by CD spectroscopy.

Original languageEnglish
Pages (from-to)960-972
Number of pages13
JournalTetrahedron Asymmetry
Volume27
Issue number19
DOIs
Publication statusPublished - Oct 15 2016

Fingerprint

Malonates
Crown Ethers
Crown ethers
Enantioselectivity
glucose
adducts
Glucose
ethers
Chalcone
catalysts
Catalysts
Chalcones
Ether
Ethers
Spectroscopy
configurations
spectroscopy

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

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title = "Crown ether derived from D-glucose as an efficient phase-transfer catalyst for the enantioselective Michael addition of malonates to enones",
abstract = "A monoaza-15-crown-5 lariat ether derived from D-glucose 1 has been applied as a chiral phase-transfer catalyst in the Michael addition of diethyl, dimethyl, diisopropyl and dibenzyl malonates to enones under mild conditions to afford the adducts with good to excellent enantioselectivities. In the reaction of diethyl malonate with substituted trans-chalcone, the adducts with in enantioselectivities up to 89{\%} ee. Among the reactions of substituted diethyl malonates, those of diethyl acetoxymalonate gave the best results (96{\%} ee). The effect of the substituents of the chalcone was also investigated in reactions with diethyl acetoxymalonate. Among the chalcones substituted on the β-aryl, the para-substituted compounds resulted in the highest enantioselectivities (88–97{\%} ee). The substituents on the benzoyl aryl of chalcone caused a decrease in the enantioselectivity compared to the unsubstituted case. The adducts with furyl or thiophenyl substituents were formed with >99{\%} ee. The glucose-based catalyst also proved to be effective in the cases of diisopropyl and dibenzyl acetoxymalonates (including ees up to 99{\%} ee). The reactions of diethyl acetoxymalonate with cyclic enones gave the corresponding Michael adducts with enantioselectivities up to 83{\%}. The absolute configuration of one of the new Michael adducts was determined by CD spectroscopy.",
author = "Zsolt Rapi and A. Gr{\"u}n and Tam{\'a}s Nemcsok and D{\'o}ra Hessz and M. K{\'a}llay and M. Kubinyi and G. Keglevich and P. Bak{\'o}",
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T1 - Crown ether derived from D-glucose as an efficient phase-transfer catalyst for the enantioselective Michael addition of malonates to enones

AU - Rapi, Zsolt

AU - Grün, A.

AU - Nemcsok, Tamás

AU - Hessz, Dóra

AU - Kállay, M.

AU - Kubinyi, M.

AU - Keglevich, G.

AU - Bakó, P.

PY - 2016/10/15

Y1 - 2016/10/15

N2 - A monoaza-15-crown-5 lariat ether derived from D-glucose 1 has been applied as a chiral phase-transfer catalyst in the Michael addition of diethyl, dimethyl, diisopropyl and dibenzyl malonates to enones under mild conditions to afford the adducts with good to excellent enantioselectivities. In the reaction of diethyl malonate with substituted trans-chalcone, the adducts with in enantioselectivities up to 89% ee. Among the reactions of substituted diethyl malonates, those of diethyl acetoxymalonate gave the best results (96% ee). The effect of the substituents of the chalcone was also investigated in reactions with diethyl acetoxymalonate. Among the chalcones substituted on the β-aryl, the para-substituted compounds resulted in the highest enantioselectivities (88–97% ee). The substituents on the benzoyl aryl of chalcone caused a decrease in the enantioselectivity compared to the unsubstituted case. The adducts with furyl or thiophenyl substituents were formed with >99% ee. The glucose-based catalyst also proved to be effective in the cases of diisopropyl and dibenzyl acetoxymalonates (including ees up to 99% ee). The reactions of diethyl acetoxymalonate with cyclic enones gave the corresponding Michael adducts with enantioselectivities up to 83%. The absolute configuration of one of the new Michael adducts was determined by CD spectroscopy.

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