Reaction of β-Nitrostyrene with Diethyl Malonate in the Presence of Bispidines: The Unusual Role of the Organocatalyst

Dalinger, Alexander I.; Mamedova, Sabina F.; Burykina, Julia V.; Pentsak, Evgeniy O.; Vatsadze, Sergey Z.

doi:10.3390/chemistry6030023

Open AccessArticle

Reaction of β-Nitrostyrene with Diethyl Malonate in the Presence of Bispidines: The Unusual Role of the Organocatalyst

by

Alexander I. Dalinger

¹

,

Sabina F. Mamedova

²,

Julia V. Burykina

¹

,

Evgeniy O. Pentsak

¹

and

Sergey Z. Vatsadze

^1,*

¹

N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, 119991 Moscow, Russia

²

Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory, MSU, 1-3, 119991 Moscow, Russia

^*

Author to whom correspondence should be addressed.

Chemistry 2024, 6(3), 387-406; https://doi.org/10.3390/chemistry6030023

Submission received: 9 April 2024 / Revised: 2 May 2024 / Accepted: 7 May 2024 / Published: 10 May 2024

(This article belongs to the Special Issue Future Trends in Catalytic Organic Synthesis)

Download

Browse Figures

Versions Notes

Abstract

The aim of this work was the investigation of novel organocatalysts for the Michael addition of diethyl malonate to β-nitrostyrene. The methodology of the study included NMR titration, reaction monitoring by NMR spectroscopy and electrospray ionization mass spectrometry (ESI-MS), product characterization by MALDI, IR spectroscopy, scanning electron microscopy (SEM), thermal gravimetric analysis (TGA), and elemental analysis. As a result, evidence of supramolecular interactions between two pairs of components of the reaction was found. In addition to the supramolecular complexes, an unusual reaction, i.e., the Michael addition of NH-bispidines to β-nitrostyrene, was found, which led to previously unknown oligomers of β-nitrostyrene. A new mechanism for the catalytic action of NH-bispidine was proposed, which involved catalysis not by the initial organocatalyst but rather by its adduct with β-nitrostyrene. Thus, in this reaction, N-benzylbispidine acted as an initiator, and the real catalyst was the betaine formed during the initiation stage.

Keywords: catalysis; bispidines; monoterpenoids; Michael addition; nitroolefins; β-nitrostyrene; NMR spectroscopy; mass-spectrometry; oligomerization

Graphical Abstract

Share and Cite

MDPI and ACS Style

Dalinger, A.I.; Mamedova, S.F.; Burykina, J.V.; Pentsak, E.O.; Vatsadze, S.Z. Reaction of β-Nitrostyrene with Diethyl Malonate in the Presence of Bispidines: The Unusual Role of the Organocatalyst. Chemistry 2024, 6, 387-406. https://doi.org/10.3390/chemistry6030023

AMA Style

Dalinger AI, Mamedova SF, Burykina JV, Pentsak EO, Vatsadze SZ. Reaction of β-Nitrostyrene with Diethyl Malonate in the Presence of Bispidines: The Unusual Role of the Organocatalyst. Chemistry. 2024; 6(3):387-406. https://doi.org/10.3390/chemistry6030023

Chicago/Turabian Style

Dalinger, Alexander I., Sabina F. Mamedova, Julia V. Burykina, Evgeniy O. Pentsak, and Sergey Z. Vatsadze. 2024. "Reaction of β-Nitrostyrene with Diethyl Malonate in the Presence of Bispidines: The Unusual Role of the Organocatalyst" Chemistry 6, no. 3: 387-406. https://doi.org/10.3390/chemistry6030023

APA Style

Dalinger, A. I., Mamedova, S. F., Burykina, J. V., Pentsak, E. O., & Vatsadze, S. Z. (2024). Reaction of β-Nitrostyrene with Diethyl Malonate in the Presence of Bispidines: The Unusual Role of the Organocatalyst. Chemistry, 6(3), 387-406. https://doi.org/10.3390/chemistry6030023

Article Menu

Reaction of β-Nitrostyrene with Diethyl Malonate in the Presence of Bispidines: The Unusual Role of the Organocatalyst

Abstract

Share and Cite

Article Metrics

Article Access Statistics

Further Information

Guidelines

MDPI Initiatives

Follow MDPI