140635-77-4

Upstream product

• 3143-02-0 3-hydroxymethyl-3-methyloxethane 
• 100-09-4 4-methoxybenzoic acid 
• 62-23-7 4-nitro-benzoic acid 
• 122-04-3 4-nitro-benzoyl chloride 

Downstream Products

• 497870-47-0 4-methyl-1-(4-nitrophenyl)-2,6,7-trioxabicyclo[2.2.2]octane 
• 72116-56-4 3-(methylthio)-6-(4-nitrophenyl)-1,2,4,5-tetrazine 
• 140635-81-0 3-methyl-3-(4-trifluoroacetamidobenzoyloxymethyl)oxetane 
• 140635-80-9 3-bromo-2-(hydroxymethyl)-2-methyl-n-propyl 4-amino-3,5-dibromobenzoate 
• 140635-79-6 3-methyl-3-(4-amino-3,5-dibromobenzoyloxymethyl)oxetane 
• 140635-78-5 3-methyl-3-(4-aminobenzoyloxymethyl)oxetane 

Relevant academic research and scientific papers

REAGENTS AND METHODS FOR TETRAZINE SYNTHESIS

Disclosed herein are mono- and di-substituted tetrazines and methods of their preparation and converting an oxetanyl ester to a thio-substituted tetrazine, which is then converted to a mono-substituted tetrazine, a di-substituted tetrazine, or a vinylether disubstituted tetrazine.

Divergent Synthesis of Monosubstituted and Unsymmetrical 3,6-Disubstituted Tetrazines from Carboxylic Ester Precursors

Since tetrazines are important tools to the field of bioorthogonal chemistry, there is a need for new approaches to synthesize unsymmetrical and 3-monosubstituted tetrazines. Described here is a general, one-pot method for converting (3-methyloxetan-3-yl)methyl carboxylic esters into 3-thiomethyltetrazines. These versatile intermediates were applied to the synthesis of unsymmetrical tetrazines through Pd-catalyzed cross-coupling and in the first catalytic thioether reduction to access monosubstituted tetrazines. This method enables the development of new tetrazine compounds possessing a favorable combination of kinetics, small size, and hydrophilicity. It was applied to a broad range of aliphatic and aromatic ester precursors and to the synthesis of heterocycles including BODIPY fluorophores and biotin. In addition, a series of tetrazine probes for monoacylglycerol lipase (MAGL) were synthesized and the most reactive one was applied to the labeling of endogenous MAGL in live cells.

Isomerization of cyclic ethers having a carbonyl functional group: New entries into different heterocyclic compounds

Oxiranes (epoxides) and oxetanes having a carbonyl functional group are chemoselectively isomerized to different heterocyclic compounds via Lewis acid-promoted 1,6- and 1,7-intramolecular nucleophilic attacks of the carbonyl oxygen on the electron-deficient carbon neighboring the oxonium oxygen: for example, cyclic imides to bicyclic acetals, esters to bicyclic orthoesters, sec-amides to 4,5-dihydrooxazole or 5,6-dihydro-4H-1,3-oxazines, and tert-amides to bicyclic acetals or azetidines. The intramolecular attack of a 1,5-positioned carbonyl oxygen predominantly results in a propagating-end isomerization polymerization. On the other hand, cyclic ethers having a 1,8- or farther positioned carbonyl group undergo conventional ring-opening polymerization. A tetrahydrofuran (oxolane) ring does not open, even with a 1,6-positioned carbonyl group.

A PRACTICAL SYNTHESIS OF ISOTOPICALLY LABELLED 1-(4-ISOTHIOCYANATOPHENYL)-4-(t-BUTYL)-2,6,7-TRIOXABICYCLOOCTANE, A PROBE FOR THE BENZODIAZEPINE RECEPTOR-COUPLED CHLORIDE IONOPHORE

An efficient synthesis of high specific activity 1-(4-isothiocyanato-3,5-ditritiophenyl)-4-(t-butyl)-2,6,7-trioxabicyclooctane (-1), an affinity ligand for the benzodiazepine (BZ)-coupled γ-aminobutyric acid (GABA)-gated chloride channel, w