Browse
Submit Data
Databases
API
Help

Dataset Information

15 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

High yielding synthesis of 2,2'-bipyridine macrocycles, versatile intermediates in the synthesis of rotaxanes.

ABSTRACT: We present an operationally simple approach to 2,2'-bipyridine macrocycles. Our method uses simple starting materials to produce these previously hard to access rotaxane precursors in remarkable yields (typically >65%) across a range of scales (0.1-5 mmol). All of the macrocycles reported are efficiently converted (>90%) to rotaxanes under AT-CuAAC conditions. With the requisite macrocycles finally available in sufficient quantities, we further demonstrate their long term utility through the first gram-scale synthesis of an AT-CuAAC [2]rotaxane and extend this powerful methodology to produce novel Sauvage-type molecular shuttles.

SUBMITTER: Lewis JEM

PROVIDER: S-EPMC6005271 | biostudies-literature | 2016 May

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

High yielding synthesis of 2,2'-bipyridine macrocycles, versatile intermediates in the synthesis of rotaxanes.

Lewis J E M JEM Bordoli R J RJ Denis M M Fletcher C J CJ Galli M M Neal E A EA Rochette E M EM Goldup S M SM

Chemical science 20160127 5

We present an operationally simple approach to 2,2'-bipyridine macrocycles. Our method uses simple starting materials to produce these previously hard to access rotaxane precursors in remarkable yields (typically >65%) across a range of scales (0.1-5 mmol). All of the macrocycles reported are efficiently converted (>90%) to rotaxanes under AT-CuAAC conditions. With the requisite macrocycles finally available in sufficient quantities, we further demonstrate their long term utility through the fir ...[more]

PMID: 29997807

Similar Datasets

2,2'-Bipyridine-Modified Tamoxifen: A Versatile Vector for Molybdacarboranes.

Project description:Investigations on the antitumor activity of metallacarboranes are sparse in the literature and limited to a handful of ruthena- and molybdacarboranes. In this study, the molybdacarborane fragment [3-(CO)2 -closo-3,1,2-MoC2 B9 H11 ] was combined with a vector molecule, inspired by the well-known drug tamoxifen or 4,4'-dihydroxytamoxifen (TAM-diOH). The molybdacarborane derivative [3,3-{4-[1,1-bis(4-hydroxyphenyl)but-1-en-2-yl]-2,2'-bipyridine-κ2 N,N'}-3-(CO)2 -closo-3,1,2-MoC2 B9 H11 ] (10), as well as the ligand itself 4-[1,1-bis(4-hydroxyphenyl)but-1-en-2-yl]-2,2'-bipyridine (6) showed cytotoxic activities in the low micromolar range against breast adenocarcinoma (MDA-MB-231, MDA-MB-361 and MCF-7), human glioblastoma (LN-229) and human glioma (U-251) cell lines. In addition, compounds 6 and 10 were found to induce senescence and cytodestructive autophagy, lower ROS/RNS levels, but only the molybdacarborane 10 induced a strong increase of nitric oxide (NO) concentration in the MCF-7 cells.

| S-EPMC6972990 | biostudies-literature

Squaraine rotaxanes with boat conformation macrocycles.

Project description:Mechanical encapsulation of fluorescent, deep-red bis(anilino)squaraine dyes inside Leigh-type tetralactam macrocycles produces interlocked squaraine rotaxanes. The surrounding macrocycles are flexible and undergo rapid exchange of chair and boat conformations in solution. A series of X-ray crystal structures show how the rotaxane co-conformational exchange process involves simultaneous lateral oscillation of the macrocycle about the center of the encapsulated squaraine thread. Rotaxane macrocycles with 1,4-phenylene sidewalls and 2,6-pyridine dicarboxamide bridging units are more likely to adopt boat conformations in the solid state than analogous squaraine rotaxane systems with isophthalamide-containing macrocycles. A truncated squaraine dye, with a secondary amine attached directly to the central C(4)O(2) core, is less electrophilic than the extended bis(anilino)squaraine analogue, but it is still susceptible to chemical and photochemical bleaching. Its stability is greatly enhanced when it is encapsulated as an interlocked squaraine rotaxane. An X-ray crystal structure of this truncated squaraine rotaxane shows the macrocycle in a boat conformation, and NMR studies indicate that the boat is maintained in solution. Encapsulation as a rotaxane increases the dye's brightness by a factor of 6. The encapsulation process appears to constrain the dye and reduce deformation of the chromophore from planarity. This study shows how mechanical encapsulation as a rotaxane can be used as a rational design parameter to fine-tune the chemical and photochemical properties of squaraine dyes.

| S-EPMC2847772 | biostudies-literature

Synthesis of Substituted 2,2'-Dinitrobiphenyls by a Novel Solvent-Free High Yielding Ullmann Coupling Biarylation.

Project description:Solvent-free reaction using a high-speed ball milling technique has been applied to the classical Ullmann coupling reaction for the first time. Biarylation of 2-iodonitrobenzene was achieved in quantitative yield when performed in a custom-made copper vial through continuous shaking without additional copper or solvent. The product was solid, NMR ready and required no lengthy extraction for purification. This reaction was cleaner, and faster than solution phase coupling which requires longer reaction time in high boiling solvents, added copper catalyst, and lengthy extraction and purification steps. Gram quantities of the biaryl compound were synthesized in larger copper vials. This is a general method that can be used to effectively reduce industrial waste en route to sustainability.

| S-EPMC4880406 | biostudies-literature

Bis(2,2'-bipyridine)(5,5'-imino-ditetra-zolato)cadmium(II) 2,2'-bipyridine hemisolvate monohydrate.

Project description:The title complex, [Cd(C(2)HN(9))(C(10)H(8)N(2))(2)]·0.5C(10)H(8)N(2)·H(2)O, was prepared under hydro-thermal reaction conditions. The asymmetric unit contains the cadmium complex, half a 2,2'-bipyridine solvent mol-ecule and a solvent water mol-ecule. The Cd(II) ion is coordinated by four N atoms from two 2,2'-bipyridine ligands and two N atoms from an HBTA(-) anion ligand [where H(2)BTA is N,N-bis-(1H-tetra-zol-5-yl)amine], forming an octa-hedral geometry. The complex is linked into a three-dimensional network by O-H?N and N-H?N hydrogen bonds and by the stacking inter-actions of rings, with distances of 3.5-3.7?Å between the atoms of two parallel 2,2'-bipyridine rings.

| S-EPMC2915158 | biostudies-literature

5,5'-Dimethyl-2,2'-bipyridine.

Project description:The asymmetric unit of the title compound, C(12)H(12)N(2), contains two half-mol-ecules related by an inversion center, the planes of their pyridine rings being oriented at a dihedral angle of 69.62?(4)°. In the crystal structure, a ?-? contact between the pyridine rings [centroid-centroid distance = 3.895?(3)?Å] may stabilize the structure. A weak C-H?? inter-action is also found.

| S-EPMC2969272 | biostudies-literature

2,2'-Dimethyl-4,4'-bipyridine.

Project description:In the crystal structure of the title compound, C(12)H(12)N(2), the mol-ecule is twisted around the central C-C bond, with a dihedral angle of 8.32?(5)° between the mean planes of the pyridyl rings. The crystal structure is stabilized by arene stacking inter-actions, with a distance of 3.81?(1)?Å between the ring centroids.

| S-EPMC2961716 | biostudies-literature

Poly[diaqua-bis(2,2'-bipyridine)tris-(?(4)-2,2'-bipyridine-4,4'-dicarboxyl-ato)dineodymium(III)].

Project description:In the crystal structure of the title mixed-ligand coordination polymer, [Nd(2)(C(12)H(6)N(2)O(4))(3)(C(10)H(8)N(2))(2)(H(2)O)(2)](n), the Nd(III) ion is in an octa-hedral coordination environment formed by one water mol-ecule, one chelating 2,2'-bipyridine ligand, and five monodentate carboxyl-ate groups. The local coordination polyhedron around the Nd(III) ion is a bicapped trigonal prism. Two Nd(III) centers are bridged by four carboxyl-ate groups to form an Nd(2) dimeric unit; these are further connected by 2,2'-bipyridine-4,4'-dicarboxyl-ate linkers, resulting in a layered coordination network.

| S-EPMC2915173 | biostudies-literature

An improved procedure for the preparation of Ru(bpz)3(PF6)2 via a high-yielding synthesis of 2,2'-bipyrazine.

Project description:There has been a recent surge of interest in the use of transition metal polypyridyl complexes as visible light-absorbing photocatalysts for synthetic applications. Among the most attractive features of this approach is the availability of many known complexes with well-characterized photophysical and electrochemical properties. In particular, Ru(bpz)3 (2+) is a powerful photooxidant that has proven to be uniquely suited for oxidatively induced photoredox transformations. We present here a straightforward and high-yielding route to Ru(bpz)3(PF6)2 that features an improved Pd-catalyzed synthesis of the 2,2'-bipyrazine ligand that is amenable to gram-scale preparations.

| S-EPMC4311765 | biostudies-literature

2,2'-Bipyridine-5,5'-dicarboxylic acid.

Project description:The title mol-ecule, C(12)H(8)N(2)O(4), lies on an inversion center. In the crystal structure, inter-molecular O-H⋯O hydrogen bonds connect mol-ecules into one-dimensional chains along [11].

| S-EPMC2969984 | biostudies-literature

Bis(?-2,2'-disulfanediyldibenzoato)bis-[aqua-(2,2'-bipyridine)-nickel(II)].

Project description:In the centrosymmetric title complex, [Ni(2)(C(14)H(8)O(4)S(2))(2)(C(10)H(8)N(2))(2)(H(2)O)(2)], the Ni(II) atom is coordinated by two N atoms from one 2,2'-bipyridine ligand, three carboxyl-ate O atoms (one bidentate and one monodentate) from two different disulfanediyldibenzoate ligands and one O atom from a coordinated water mol-ecule in an octa-hedral coordination geometry. The disulfanediyldibenzo-ate dianion bridges two Ni(II )atoms. Adjacent mol-ecules are linked through the coordinated water mol-ecules, forming a O-H?O hydrogen-bonded chain running along the a axis.

| S-EPMC3011661 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data