Bioorthogonal Tetrazine Carbamate Cleavage by Highly Reactive trans-Cyclooctene. 2020

Arthur H A M van Onzen, and Ron M Versteegen, and Freek J M Hoeben, and Ivo A W Filot, and Raffaella Rossin, and Tong Zhu, and Jeremy Wu, and Peter J Hudson, and Henk M Janssen, and Wolter Ten Hoeve, and Marc S Robillard
Tagworks Pharmaceuticals, Geert Grooteplein Zuid 10, 6525 GA Nijmegen, The Netherlands.

The high rate of the 'click-to-release' reaction between an allylic substituted trans-cyclooctene linker and a tetrazine activator has enabled exceptional control over chemical and biological processes. Here we report the development of a new bioorthogonal cleavage reaction based on trans-cyclooctene and tetrazine, which allows the use of highly reactive trans-cyclooctenes, leading to 3 orders of magnitude higher click rates compared to the parent reaction, and 4 to 6 orders higher than other cleavage reactions. In this new pyridazine elimination mechanism, wherein the roles are reversed, a trans-cyclooctene activator reacts with a tetrazine linker that is substituted with a methylene-linked carbamate, leading to a 1,4-elimination of the carbamate and liberation of a secondary amine. Through a series of mechanistic studies, we identified the 2,5-dihydropyridazine tautomer as the releasing species and found factors that govern its formation and subsequent fragmentation. The bioorthogonal utility was demonstrated by the selective cleavage of a tetrazine-linked antibody-drug conjugate by trans-cyclooctenes, affording efficient drug liberation in plasma and cell culture. Finally, the parent and the new reaction were compared at low concentration, showing that the use of a highly reactive trans-cyclooctene as the activator leads to a complete cycloaddition reaction with the antibody-drug conjugate in seconds vs hours for the parent system. Although the subsequent release from the IEDDA adduct is slower, we believe that this new reaction may allow markedly reduced click-to-release reagent doses in vitro and in vivo and could expand the application scope to conditions wherein the trans-cyclooctene has limited stability.

UI MeSH Term Description Entries
D009842 Oligopeptides Peptides composed of between two and twelve amino acids. Oligopeptide
D011355 Prodrugs A compound that, on administration, must undergo chemical conversion by metabolic processes before becoming the pharmacologically active drug for which it is a prodrug. Drug Precursor,Drug Precursors,Pro-Drug,Prodrug,Pro-Drugs,Precursor, Drug,Precursors, Drug,Pro Drug,Pro Drugs
D011724 Pyridazines Six-membered rings with two adjacent nitrogen atoms also called 1,2-diazine.
D002219 Carbamates Derivatives of carbamic acid, H2NC( Carbamate,Aminoformic Acids,Carbamic Acids,Acids, Aminoformic,Acids, Carbamic
D006801 Humans Members of the species Homo sapiens. Homo sapiens,Man (Taxonomy),Human,Man, Modern,Modern Man
D000075082 Proof of Concept Study An empirical investigation which pertains to the development of prototypes or models that demonstrate the feasibility of novel concepts, ideas, principles, schema or their practical application. Proof of Concept Approach,Proof of Concept Demonstration,Proof of Concept Evaluation,Proof of Concept Experiment,Proof of Concept Investigation,Proof of Concept Model,Proof of Concept Prototype,Proof of Concept Research,Proof of Concept Studies,Proof of Concept Testing,Approach Proof, Concept,Approach Proofs, Concept,Concept Approach Proof,Concept Approach Proofs,Concept Demonstration Proof,Concept Evaluation Proof,Concept Evaluation Proofs,Concept Experiment Proof,Concept Experiment Proofs,Concept Investigation Proof,Concept Model Proof,Concept Model Proofs,Concept Prototype Proof,Concept Prototype Proofs,Concept Research Proof,Concept Research Proofs,Concept Study Proof,Concept Testing Proof,Concept Testing Proofs,Demonstration Proof, Concept,Evaluation Proof, Concept,Experiment Proof, Concept,Investigation Proof, Concept,Model Proof, Concept,Prototype Proof, Concept,Research Proof, Concept,Study Proof, Concept,Testing Proof, Concept,Testing Proofs, Concept
D000970 Antineoplastic Agents Substances that inhibit or prevent the proliferation of NEOPLASMS. Anticancer Agent,Antineoplastic,Antineoplastic Agent,Antineoplastic Drug,Antitumor Agent,Antitumor Drug,Cancer Chemotherapy Agent,Cancer Chemotherapy Drug,Anticancer Agents,Antineoplastic Drugs,Antineoplastics,Antitumor Agents,Antitumor Drugs,Cancer Chemotherapy Agents,Cancer Chemotherapy Drugs,Chemotherapeutic Anticancer Agents,Chemotherapeutic Anticancer Drug,Agent, Anticancer,Agent, Antineoplastic,Agent, Antitumor,Agent, Cancer Chemotherapy,Agents, Anticancer,Agents, Antineoplastic,Agents, Antitumor,Agents, Cancer Chemotherapy,Agents, Chemotherapeutic Anticancer,Chemotherapy Agent, Cancer,Chemotherapy Agents, Cancer,Chemotherapy Drug, Cancer,Chemotherapy Drugs, Cancer,Drug, Antineoplastic,Drug, Antitumor,Drug, Cancer Chemotherapy,Drug, Chemotherapeutic Anticancer,Drugs, Antineoplastic,Drugs, Antitumor,Drugs, Cancer Chemotherapy
D001372 Aza Compounds Organic chemicals where carbon atoms have been replaced by nitrogen atoms. Compounds, Aza
D001555 Benzene Derivatives Organic compounds derived from BENZENE. Derivatives, Benzene
D045744 Cell Line, Tumor A cell line derived from cultured tumor cells. Tumor Cell Line,Cell Lines, Tumor,Line, Tumor Cell,Lines, Tumor Cell,Tumor Cell Lines

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