Synthesis and determination of alkali metal binding selectivities of chiral macrocyclic bisamides derived from d-mannitol and l-threitol possessing 2,6-pyridinedicarboxamide subunits

doi:10.1016/j.tetasy.2005.04.028

Tetrahedron: Asymmetry

Volume 16, Issue 11, 6 June 2005, Pages 1939-1946

https://doi.org/10.1016/j.tetasy.2005.04.028 Get rights and content

Abstract

Five chiral macrocyclic bisamides derived from d-mannitol and l-threitol, possessing C₂ symmetry, were obtained by a macrocyclization reaction under two different conditions (MeOH, 12 kbar, rt or MeONa/MeOH, 1 bar, rt). Their applications for alkali metal binding processes are studied using ESI-MS technique.

Graphical abstract

Introduction

The chiral recognition and complexation properties of natural receptors have attracted considerable attention due to the design and synthesis of new chiral macrocyclic rings, for example, poliaza¹ and polyoxacoronands.² In the early 1990s, we found that α,ω-diaminoethers reacted under ambient conditions with dimethyl α,ω-dicarboxylates in methanol as a solvent, to afford the macrocyclic bisamides.³ This method was also extensively investigated by using the high-pressure technique.⁴ The amide group exhibits a dual complexing feature (C double bond O and N or NH), thus meaning amide-based molecular receptors can bind metal⁵ and ammonium cations,⁶ neutral organic molecules⁷ as well as anionic species.⁸ Moreover, macrocyclic bisamides can be synthesized in their optically active forms and applied to chiral recognition processes.⁹ Recently, we published10, 11 an effective method for the synthesis of chiral bisamides using α,ω-diamines derived from d-mannitol and l-threitol. In contrast to achiral macrocyclic compounds, the synthesis of their chiral analogs is more difficult due to use of chiral α,ω-diaminoethers as substrates. Three diaminoethers 2–4 have been prepared by us previously.¹⁰ Herein, we report a useful synthetic way of preparing their analog 1. All four C₂-symmetric α,ω-diaminoethers containing three or five ethylene units were applied for macrocyclization reactions leading to eight chiral bisamides. Electrospray ionization mass spectrometry (ESI-MS) was used to evaluate the alkali metal binding selectivities of these chiral bisamide compounds possessing 2,6-pyridine subunits.

Section snippets

Synthesis

1,2;5,6-Di-O-isopropylidene-d-mannitol and 1,4-di-O-benzyl-l-threitol were selected as inexpensive and convenient sources of chirality. These readily available building blocks were used for the synthesis of numerous chiral coronands.¹² The synthesis of d-mannitol-derived α,ω-diaminoethers 2 and 4 containing three and five ethylene units and l-threitol-derived α,ω-diaminoether 3 possessing five ethylene units have been already reported¹⁰ (Fig. 1).

The synthesis of l-threitol-derived

Conclusions

As a result of our investigation, a new efficient method of macrocyclization leading to chiral macrocyclic bisamides has been developed. Moreover, we demonstrated that the ESI-MS technique can be successfully used for the preliminary determination of the selectivity of binding of the alkali metal cations by the prepared macrocyclic compounds.

General methods

Melting points were taken on a Köfler-type (Boetius) hot-stage apparatus and are uncorrected. Optical rotations were measured using a Perkin–Elmer 241 polarimeter equipped with a thermally-jacketed 10 cm cell. ¹H NMR spectra were recorded with a Varian Gemini 200 (200 MHz) or a Varian Gemini 500 (500 MHz) spectrometer in CDCl₃ using tetramethylsilane as an internal standard. ¹³C NMR spectra were also recorded using a Varian Gemini 200 (50 MHz) or a Varian Gemini 500 (125 MHz) spectrometer. All

Acknowledgments

This work was supported by the State Committee for Scientific Research (Project T09A 087 21). The authors wish to thank the Polish Science Foundation for additional financial support.

References (27)

M. Achmatowicz et al.
Tetrahedron: Asymmetry
(2001)
T. Zieliński et al.
Tetrahedron: Asymmetry
(2002)
J. Jurczak et al.
Tetrahedron
(1993)
D.T. Gryko et al.
Tetrahedron
(1998)
D.T. Gryko et al.
Supramol. Chem.
(2000)
V.P. Solov’ev et al.
Eur. J. Org. Chem.
(1998)
T. Pigot et al.
J. Chem. Soc., Perkin Trans. 2
(1993)
P. Bakó et al.
Liebigs Ann. Chem.
(1990)
E.C. Kempen et al.
Anal. Chem.
(1999)
S.A. Hofstadler et al.
Chem. Rev.
(2001)
S.M. Blair et al.
J. Am. Soc. Mass Spectrom.
(2000)
R. Bakhtiar et al.
Rapid Commun. Mass Spectrom.
(1997)
J. Jurczak et al.
High Press. Res.
(1992)
A.Y. Nazarenko et al.
J. Incl. Phenom.
(1995)
P. Huszthy et al.
J. Org. Chem.
(1992)

F.G. Tellado et al.

J. Am. Chem. Soc.

(1990)

S.K. Chang et al.

J. Am. Chem. Soc.

(1988)

A.P. Davis et al.

J. Am. Chem. Soc.

(1997)

T.R. Kelly et al.

J. Am. Chem. Soc.

(1994)

R.M. Izatt et al.

Chem. Rev.

(1992)

Cited by (8)

EDC/DMAP-mediated direct condensation of dicarboxylic acids and diols: A concise synthesis of extra large polyether macrocyclic lactones and their X-ray structures
2016, Tetrahedron Letters
We report the EDC/DMAP-mediated direct condensation reactions of dicarboxylic acids with diols and synthesis of new classes of 18-48-membered, small and extra-large polyether macrocyclic lactones. The methodology was executed by using various dicarboxylic acids linked via aliphatic, polyether and aromatic linkers and different diols (e.g., (Z)-but-2-ene-1,4-diol, but-2-yne-1,4-diol, 2,2′-thiobis(ethan-1-ol), 2,2′-(benzylazanediyl)bis(ethan-1-ol), 2,2′-oxybis(ethan-1-ol)). The condensation reactions of dicarboxylic acids with diols afforded 1:1 (18-24-membered) and 2:2 (36–48-membered) polyether macrocyclic lactones. The synthesis of small and extra-large polyether macrocyclic lactones was accomplished without using a template and relatively simple reaction conditions. All the reported macrocyclic lactones were separated by column chromatography and characterized by ¹H, ¹³C NMR and HRMS analyses. The solid state (X-ray) structures of representative polyether macrocyclic lactones were also reported.
Probing the structural changes accompanying a spin crossover transition in a chiral [Fe(II)(N<inf>3</inf>O<inf>2</inf>)(CN)<inf>2</inf>] macrocycle by X-ray crystallography
2015, CrystEngComm
An optimized synthetic route for the preparation of the versatile chiral building block 1,4-di-O-benzylthreitol
2014, Monatshefte fur Chemie
Synthesis, structural characterization and metal inclusion properties of 18-, 20- and 22-membered oxaazacyclophanes and oxaazacalix[4]arene analogues: Macrocyclic amine and schiff base receptors with variable N<inf>x</inf>O <inf>y</inf> donor sets
2011, European Journal of Organic Chemistry
Mitsunobu and Related Reactions: Advances and Applications
2009, Chemical Reviews
Synthesis of a Series of Novel Chiral Aromatic Heterocyclic Macrocycles Containing L-Amino Acid and 2,5-Bisphenyl-1,3,4-triazole Subunits
2009, Synthetic Communications

View all citing articles on Scopus

View full text

Synthesis and determination of alkali metal binding selectivities of chiral macrocyclic bisamides derived from d-mannitol and l-threitol possessing 2,6-pyridinedicarboxamide subunits

Abstract

Graphical abstract

Introduction

Section snippets

Synthesis

Conclusions

General methods

Acknowledgments

Tetrahedron: Asymmetry

Tetrahedron: Asymmetry

Tetrahedron

Tetrahedron

Supramol. Chem.

Eur. J. Org. Chem.

J. Chem. Soc., Perkin Trans. 2

Liebigs Ann. Chem.

Anal. Chem.

Chem. Rev.

J. Am. Soc. Mass Spectrom.

Rapid Commun. Mass Spectrom.

High Press. Res.

J. Incl. Phenom.

J. Org. Chem.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

Chem. Rev.