Efficient solid support catalyzed mono-aza-Michael addition
reactions of piperazine

J 2015

Efficient solid support catalyzed mono-aza-Michael addition reactions of piperazine

HEROVÁ, Dana and Pavel PAZDERA

Basic information

Original name

Efficient solid support catalyzed mono-aza-Michael addition reactions of piperazine

Authors

HEROVÁ, Dana (203 Czech Republic, belonging to the institution) and Pavel PAZDERA (203 Czech Republic, guarantor, belonging to the institution)

Edition

Monatshefte für Chemie - Chemical Monthly, 2015, 0026-9247

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10401 Organic chemistry

Country of publisher

Austria

Confidentiality degree

není předmětem státního či obchodního tajemství

Impact factor

Impact factor: 1.131

RIV identification code

RIV/00216224:14310/15:00081733

Organization unit

Faculty of Science

DOI

http://dx.doi.org/10.1007/s00706-014-1379-2

UT WoS

000351279800015

Keywords in English

Aza-Michael addition; Catalysis; Metal catalysis; One-pot synthesis; Resin-supported metal ion

Abstract

V originále

We report new methods for the efficient mono-aza-Michael additions of piperazine to compounds with activated multiple carbon–carbon bond (functional derivatives of acrylic, propiolic, and acetylenedicarboxylic acid). This method is based on the reaction of piperazine-1-ium cation with alkenes or alkynes substituted by EWGs under catalysis by various metal ions supported on weakly acidic cation-exchanger resin. Starting piperazine-1-ium cation is generated in situ in methanol solution by mixing of piperazine and piperazine-1,4-diium dichloride in various ratios. It was found that solid support metal catalysis afforded target products in very good yields in shortened reaction times. A new method of N-monosubstituted piperazine derivative preparation is very beneficial, because until now no one has come up with the idea to use for protection of the one nitrogen atom of the piperazine its simple protonation. Computer modeling of behavior of piperazine depending on the pH was carried out and according to the results, we concluded that the protonation of the nitrogen atom is the simplest, most effective, and most elegant method of preventing unwanted formation of 1,4-disubstituted product. Assumption was fully confirmed by number of syntheses. The main advantages of our syntheses are great simplicity, one-pot performance, use of non-toxic solvents only, mild reaction conditions, no generation of waste, short time of reactions, and high yields.

Links

2A-1TP1/090, research and development project

Name: Nové katalyzátory a činidla pro udržitelné zelené syntézy a kombinatoriální syntézy.

Investor: Ministry of Industry and Trade of the CR, New catalysts and reagents for sustainable green syntheses and combinatorial syntheses

Citovat

HEROVÁ, Dana and Pavel PAZDERA. Efficient solid support catalyzed mono-aza-Michael addition reactions of piperazine. Monatshefte für Chemie - Chemical Monthly. 2015, vol. 146, No 4, p. 653-661. ISSN 0026-9247. Available from: https://dx.doi.org/10.1007/s00706-014-1379-2.

@article{1217978,
   author = {Herová, Dana and Pazdera, Pavel},
   article_number = {4},
   doi = {http://dx.doi.org/10.1007/s00706-014-1379-2},
   keywords = {Aza-Michael addition; Catalysis; Metal catalysis; One-pot synthesis; Resin-supported metal ion},
   language = {eng},
   issn = {0026-9247},
   journal = {Monatshefte für Chemie - Chemical Monthly},
   title = {Efficient solid support catalyzed mono-aza-Michael addition reactions of piperazine},
   volume = {146},
   year = {2015}
}

TY  - JOUR
ID  - 1217978
AU  - Herová, Dana - Pazdera, Pavel
PY  - 2015
TI  - Efficient solid support catalyzed mono-aza-Michael addition reactions of piperazine
JF  - Monatshefte für Chemie - Chemical Monthly
VL  - 146
IS  - 4
SP  - 653-661
EP  - 653-661
SN  - 00269247
KW  - Aza-Michael addition
KW  - Catalysis
KW  - Metal catalysis
KW  - One-pot synthesis
KW  - Resin-supported metal ion
N2  - We report new methods for the efficient mono-aza-Michael additions of piperazine to compounds with activated multiple carbon–carbon bond (functional derivatives of acrylic, propiolic, and acetylenedicarboxylic acid). This method is based on the reaction of piperazine-1-ium cation with alkenes or alkynes substituted by EWGs under catalysis by various metal ions supported on weakly acidic cation-exchanger resin. Starting piperazine-1-ium cation is generated in situ in methanol solution by mixing of piperazine and piperazine-1,4-diium dichloride in various ratios. It was found that solid support metal catalysis afforded target products in very good yields in shortened reaction times. A new method of N-monosubstituted piperazine derivative preparation is very beneficial, because until now no one has come up with the idea to use for protection of the one nitrogen atom of the piperazine its simple protonation. Computer modeling of behavior of piperazine depending on the pH was carried out and according to the results, we concluded that the protonation of the nitrogen atom is the simplest, most effective, and most elegant method of preventing unwanted formation of 1,4-disubstituted product. Assumption was fully confirmed by number of syntheses. The main advantages of our syntheses are great simplicity, one-pot performance, use of non-toxic solvents only, mild reaction conditions, no generation of waste, short time of reactions, and high yields.
ER  -

HEROVÁ, Dana and Pavel PAZDERA. Efficient solid support catalyzed mono-aza-Michael addition reactions of piperazine. \textit{Monatshefte für Chemie - Chemical Monthly}. 2015, vol.~146, No~4, p.~653-661. ISSN~0026-9247. Available from: https://dx.doi.org/10.1007/s00706-014-1379-2.

Detailed Information on Publication Record