Azacalixaromatics

Wang, De‐Xian; Wang, Mei‐Xiang

doi:10.1007/978-3-319-31867-7_14

Cited by 8 publications

(8 citation statements)

References 84 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Heteracalixaromatics − are synthetic macrocycles, which are composed of heteroatoms and meta -(het)arylene in an alternative manner. Being different from conventional calix[4]arenes, nitrogen- and oxygen-bridged calix[4]aromatics reported to date adopt generally 1,3-alternate conformational structures both in crystalline state and in solution .…”

Section: Introductionmentioning

confidence: 99%

“…As a consequence, the macrocyclic cavities and, more significantly, the electronic features of 1,3-alternate heteracalix[4]aromatics are amenable to regulation by means of the interplay between different heteroatoms and diverse aromatic subunits . The unique structural advantages along with the easy availability render heteracalix[4]aromatics powerful and versatile macrocyclic host molecules in supramolecular chemistry. − For example, azacalix[4]pyridines interact selectively with both the electron neutral organic molecules such as fullerenes and the charged species including transition metal ions, while oxacalix[2]arene[2]triazines form complexes with anions of different geometries, shapes, and volumes owing to noncovalent anion-π interactions . Applications of heteracalix[4]aromatics in the fabrication of metal organic frameworks, CO 2 -absorbents, anion responsive vesicles, liquid crystals, stationary phase, and organic catalysts have also been demonstrated.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis and Structure of Functionalized Homo Heteracalix[2]arene[2]triazines: Effect of All Heteroatom Bridges on Macrocyclic Conformation

Liang

Wang

2018

J. Org. Chem.

Self Cite

View full text Add to dashboard Cite

A number of unprecedented homo heteracalix[2]arene[2]triazines were synthesized by means of a fragment coupling approach. Two directional nucleophilic substitution reactions of N-Boc-protected 1,3-dihydrazobenzene with cyanuric acid chloride and 2-butoxy-4,6-dichloro-1,3,5-triazine led to hydrazo-linked trimers, which underwent an efficient macrocyclic condensation reaction with functionalized resorcinol derivatives to afford (NHNBoc),O-calix[2]arene[2]triazine macrocycles, which contain a functional group either on the upper rim or the lower rim. The use of 1,3-phenylenediamines instead of resorcinol in the reaction produced (NR),(NHNBoc)-calix[2]arene[2]triazines. Postmacrocyclization modifications such as a nucleophilic substitution reaction of chloro on triazine by amines and the removal of Boc from hydrazo moieties produced homo calix[2]arene[2]triazine derivatives. In the solid state, (NHNR),O-bridged calix[2]arene[2]triazines with and without a substituent on the upper rim position and (NMe),(NHNBoc)-calix[2]arene[2]triazine adopted a typical partial cone conformation while the heavily twisted 1,3-alternate conformational structures were observed for both (NHNBoc),O-calix[2]arene[2]triazines bearing a functional group on the lower rim position and (NH),(NHNBoc)-calix[2]arene[2]triazine. In solution, all synthesized homo heteracalix[2]arene[2]triazines existed as the mixture of different macrocyclic conformers, which underwent slow interconversions at room temperature relative to the NMR time scale.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis and Structure of Functionalized Homo Heteracalix[2]arene[2]triazines: Effect of All Heteroatom Bridges on Macrocyclic Conformation

Liang

Wang

2018

J. Org. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

“…The spirodienone route [ 14 ] and Lhtoak’s mercuration [ 15 ] route, however, are notable exceptions for effecting the direct modifications to the basic calix[4]arene skeleton not specifically involving the functionalization of the upper and/or lower rims, or via convergent fragment-based approaches. Since there are many excellent reviews and monographs that have been published on calixarenes, and their more typical analogues, including homocalixarenes [ 16 ], homooxacalixarenes [ 17 , 18 ], azacalixarenes [ 19 ] and hexahomoazacalixarenes [ 20 ], and other types [ 21 , 22 ] the reader is referred to these so will not be further elaborated upon here. Instead, for this review, we have chosen to emphasize the MCP skeleton that has been extensively explored as a versatile and stable platform, or scaffold, for functionalization and study.…”

Section: Introductionmentioning

confidence: 99%

Calix[3]arene-Analogous Metacyclophanes: Synthesis, Structures and Properties with Infinite Potential

et al. 2020

View full text Add to dashboard Cite

Calixarene-analogous metacyclophanes (CAMs) are a special class of cyclophanes that are cyclic polyaromatic hydrocarbons containing three or more aromatic rings linked by one or more methylene bridging groups. They can be considered to be analogues of calixarenes, since, in both types of molecules, the component aromatic rings are linked by methylene groups, which are meta to each other. Since the prototype or classical calix[4]arene consists of four benzene rings each linked by methylene bridges, which are also meta to each other, it can be considered to be an example of a functionalized [1.1.1.1]metacyclophane. A metacyclophane (MCP) that consists of three individual hydroxyl-group functionalized aromatic rings linked by methylene groups, e.g., a trihydroxy[1.1.1]MCP may therefore, by analogy, be termed in the broadest sense as a “calix[3]arene” or a “calix[3]arene-analogous metacyclophane”. Most of the CAMs reported have been synthesized by fragment coupling approaches. The design, synthesis and development of functionalized CAMs, MCPs, calixarenes and calixarene analogues has been an area of great activity in the past few decades, due their potential applications as molecular receptors, sensors and ligands for metal binding, and for theoretical studies, etc. In this review article, we focus mainly on the synthesis, structure and conformational properties of [1.1.1]CAMs, i.e., “calix[3]arenes” and their analogues, which contain three functionalized aromatic rings and which provide new scaffolds for further explorations in supramolecular and sensor chemistry.

show abstract

“…Besides the classical calixarene phenolic subunits linked by methylene groups, “calixarenes” incorporating other subunits include, but are not limited to, resorcinol [ 8 ], hydroquinone [ 9 ], naphthols [ 10 ], pyrrole [ 11 ], heteroaromatics [ 12 ] and triptycene [ 13 ] in their cavity-containing structures have gained much recent attention. Among the least-studied to date, however, have been the azulene unit-containing calix[4]arene analogues.…”

Section: Introductionmentioning

confidence: 99%

Calixazulenes: azulene-based calixarene analogues – an overview and recent supramolecular complexation studies

Georghiou¹,

Rahman²,

Alodhayb³

et al. 2018

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

Some of the least studied calixarenes are those that consist of azulene rings bridged by -CH2- groups. Since Lash and Colby’s discovery of a simple and convenient method for producing the parent all-hydrocarbon calix[4]azulene, there have been two other all-hydrocarbon calix[4]azulenes which have been synthesized in good yields by their method. This allowed studying their supramolecular properties. This report is of our latest work on the solution-state supramolecular complexation of one of these calix[4]azulenes, namely tetrakis(5,7-diphenyl)calix[4]azulene or “OPC4A”, with several electron-deficient tetraalkyammonium salts. As a result of more recent methods developed by us and others employing Suzuki–Miyaura cross-coupling reactions to produce additional functionalized azulenes, the promise of further greater functionalized calixazulenes lies in store to be investigated.

show abstract

Azacalixaromatics

Cited by 8 publications

References 84 publications

Synthesis and Structure of Functionalized Homo Heteracalix[2]arene[2]triazines: Effect of All Heteroatom Bridges on Macrocyclic Conformation

Synthesis and Structure of Functionalized Homo Heteracalix[2]arene[2]triazines: Effect of All Heteroatom Bridges on Macrocyclic Conformation

Calix[3]arene-Analogous Metacyclophanes: Synthesis, Structures and Properties with Infinite Potential

Calixazulenes: azulene-based calixarene analogues – an overview and recent supramolecular complexation studies

Contact Info

Product

Resources

About