HMF in multicomponent reactions: utilization of 5-hydroxymethylfurfural (HMF) in the Biginelli reaction

HMF in multicomponent reactions: utilization of 5-hydroxymethylfurfural (HMF) in the Biginelli reaction

Green Chem., 2018, Advance Article
DOI: 10.1039/C7GC03425C, Paper

Weigang Fan, Yves Queneau, Florence Popowycz
The use of the renewable platform molecule 5-hydroxymethylfurfural (HMF) in the multi-component Biginelli reaction has been investigated.

HMF in multicomponent reactions: utilization of 5-hydroxymethylfurfural (HMF) in the Biginelli reaction

 

Weigang Fan,^a  Yves Queneau*^a  and  Florence Popowycz*^a 

http://pubs.rsc.org/en/Content/ArticleLanding/2018/GC/C7GC03425C?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

* Corresponding authors

^a Université de Lyon, INSA Lyon, ICBMS, Equipe Chimie Organique et Bioorganique, UMR 5246 CNRS, Université Lyon 1, CPE Lyon, Bâtiment Jules Verne, 20 Avenue Albert Einstein, F-69621 Villeurbanne Cedex, France
E-mail: yves.queneau@insa-lyon.fr, florence.popowycz@insa-lyon.fr

Abstract

The use of the renewable platform molecule 5-hydroxymethylfurfural (HMF) in the multi-component Biginelli reaction has been investigated. Multicomponent reactions (MCR) using HMF offer straightforward access to novel fine chemicals. However, the peculiar reactivity and lower stability of HMF have limited its use in such strategies. In this paper, we report our results on the use of HMF in 3-component Biginelli reactions, leading in one single step to a series of functionalized dihydropyrimidinones obtained in moderate to good yields, with a broad substrate scope of 1,3-dicarbonyl compounds and urea building blocks. This is the first report on the use of HMF in this reaction. The CH₂OH motif found in HMF provides useful functionalization for the target molecules, which cannot be offered by simpler aldehydes such as furfural.
5-Acetyl-4-[5’-(hydroxymethyl)furan-2’-yl]-6-methyl-3,4-dihydropyrimidin-2(1H)-one (4a):

 

Reaction time: 8 h; Global yield: 86%; (78% yield after simple filtration + additional 8% yield after purification of the filtrate by column chromatography).
1H NMR (400 MHz, DMSO-d6) δ 9.22 (d, 1H, J = 1.2 Hz, H1), 7.88 (dd, 1H, J = 3.4, 1.2 Hz, H3), 6.16 (d, 1H, J = 3.1 Hz, H4’), 6.03 (d, 1H, J = 3.1 Hz, H3’), 5.27 (d, 1H, J = 3.4 Hz, H4), 5.18 (t, 1H, J = 5.6 Hz, OH), 4.33 (d, 2H, J = 5.6 Hz, CH2), 2.25 (s, 3H, CH3-C6), 2.17 (s, 3H, CH3CO).
13C NMR (100 MHz, DMSO-d6) δ 193.9 (COCH3), 155.1, 154.9 (C2’, C5’), 152.4 (C2), 149.0 (C6), 107.7 (C4’), 107.1 (C5), 106.3 (C3’), 55.7 (CH2OH), 47.9 (C4), 30.0 (CH3CO), 19.0 (CH3-C6).
HRMS (ESI) m/z: Calcd for [M+Na]+ C12H14N2NaO4 273.0846; Found 273.0850.

Weigang Fan

Research experience

• Sep 2015–Mar 2017

  Doctorant

  Institut National des Sciences Appliquées de Lyon · Institut de Chimie et de Biochimie Moléculaires et Supramoléculaires (ICBMS - UMR 5246)
  France · Lyon

 

 

Florence POPOWYCZ

Université de Lyon, INSA Lyon, ICBMS, Equipe Chimie Organique et Bioorganique, UMR 5246 CNRS, Université Lyon 1, CPE Lyon, Bâtiment Jules Verne, 20 Avenue Albert Einstein, F-69621 Villeurbanne Cedex, France
E-mail:  florence.popowycz@insa-lyon.fr

 

 

 

Yves QUENEAU

CNRS Research Director chez ICBMS INSA Lyon Univ Lyon - Carbohydrate Chemistry

ICBMS INSA Lyon University of Lyon

 

Université de Lyon, INSA Lyon, ICBMS, Equipe Chimie Organique et Bioorganique, UMR 5246 CNRS, Université Lyon 1, CPE Lyon, Bâtiment Jules Verne, 20 Avenue Albert Einstein, F-69621 Villeurbanne Cedex, France
E-mail: yves.queneau@insa-lyon.fr,

///////////////HMF, multicomponent reactions,  5-hydroxymethylfurfural, Biginelli reaction

Multicomponent reactions: A simple and efficient route to heterocyclic phosphonates

.

Multicomponent reactions: A simple and efficient route to heterocyclic phosphonates

Mohammad Haji

Beilstein J. Org. Chem. 2016, 12, 1269–1301. published 21 Jun 2016

 

Chemistry Department, Science and Research Branch, Islamic Azad University, Tehran, Iran

 Corresponding author email     mh_1395@yahoo.com

Associate Editor: T. J. J. Müller

Beilstein J. Org. Chem. 2016, 12, 1269–1301.

doi:10.3762/bjoc.12.121

Abstract

Multicomponent reactions (MCRs) are one of the most important processes for the preparation of highly functionalized organic compounds in modern synthetic chemistry. As shown in this review, they play an important role in organophosphorus chemistry where phosphorus reagents are used as substrates for the synthesis of a wide range of phosphorylated heterocycles. In this article, an overview about multicomponent reactions used for the synthesis of heterocyclic compounds bearing a phosphonate group on the ring is given.

http://www.beilstein-journals.org/bjoc/single/articleFullText.htm?publicId=1860-5397-12-121&vt=f&tpn=0&bpn=home

Conclusion

In this article the use of different multicomponent reactions (MCRs) for the synthesis of heterocyclic phosphonates has been reviewed. This review demonstrates the synthetic potential of multicomponent reactions for the construction of phosphono-substituted heterocyclic rings. The Kabachnik–Fields reaction can be considered the starting point of multicomponent synthesis of this class of compounds. However, the major advancements in this interesting field have been achieved in recent years. More than 75% of the cited literature in this review has been published within the last six years, of which more than three quarters dealt with the synthesis of new heterocyclic phosphonates from non-heterocyclic phosphorus reagents. The remaining works reported the phosphorylation of parent heterocyclic systems. It is worth mentioning, that most of the cited publications focused on the synthesis of five and six-membered rings and only four articles described the synthesis of three and seven-membered heterocycles. Additionally, the majority of the reported syntheses were devoted to the development of new methodologies including the use of advanced catalytic systems, alternative solvents and microwave irradiation. Thus, the development of novel MCR based on phosphorous reagents would allow the synthesis of macrocyclic and medium or large-sized heterocyclic systems, substances which are currently underrepresented in the literature. Further, the design of new biocompatible scaffolds such as β-lactams and peptidomimetics possessing phosphonate groups by MCR-based strategies would significantly extend the synthetic potential of MCRs towards heterocyclic phosphonates

//////////multicomponent reactions,  organophosphorus chemistry,  phosphorus reagents,  phosphorylated heterocycles

Recent advances on diversity oriented heterocycle synthesis via multicomponent tandem reactions based on A3 coupling

Recent advances on diversity oriented heterocycle synthesis via multicomponent tandem reactions based on A³ coupling (14-8183LR) [pp. 1-20]
Arkivoc 2014 Part (i), 1-20: Special Issue 'Reviews and Accounts'
Yunyun Liu
Full Text: PDF (235K)
http://www.arkat-usa.org/get-file/48824/
Recent advances on diversity oriented heterocycle synthesis via
multicomponent tandem reactions based on A3 coupling

Yunyun Liu*
a,b

a Key Laboratory of Functional Small Organic Molecule, Ministry of Education,
Jiangxi Normal University, Nanchang 330022, P. R. China
b College of Chemistry and Chemical Engineering, Jiangxi Normal University,
Nanchang 330022, P. R. China

Abstract
A3 coupling reactions are the reactions between aldehydes, amines and alkynes, which yield
propargylamine derivatives under various catalyst conditions. By making use of the versatile
reactivity of propargylamines, tandem reactions initiated by the functional group(s) in the in situ
generated propargylamines constitute one of the most important applications of A3
 couplings.
These tandem reactions are especially useful for the synthesis of heterocyclic compounds. In this
review, the progress on multicomponent tandem reactions based on A3
 coupling is summarized.



Author’s Biography


Dr. Yunyun Liu was born in 1983 in Shandong Province, China. She obtained her Bachelor
Degree in Qufu Normal University in 2005. She then moved to Zhejiang University to continue
her graduate study in the Department of Chemistry. Under the supervision of Professor Weiliang
Bao, she worked on the field of copper-catalyzed Ullmann coupling reaction and related tandem
reactions for her doctorate study. She obtained her doctorate degree in 2010 and presently she is
an assistant professor in Jiangxi Normal University. She is currently interested in the research of
metal-catalyzed organic synthesis and the development of new cascade organic reactions.