Methods for inducing bioorthogonal reactivity

Patent metadata

Field	Value
Publication number	US-10875840-B2
Application number	US-201616062423-A
Country	US
Kind code	B2
Filing date	Dec 15, 2016
Priority date	Dec 15, 2015
Publication date	Dec 29, 2020
Grant date	Dec 29, 2020

Abstract

A method for catalytically converting a dihydrotetrazine 1 into a tetrazine 2, wherein one R group on the dihydrotetrazine 1 is a substituted or unsubstituted aryl, heteroaryl, alkyl, alkenyl, alkynyl, carbonyl, or heteroatom-containing group, and the other R group is selected from the group consisting of H and substituted or unsubstituted aryl, heteroaryl, alkyl, alkenyl, alkynyl, carbonyl,- or heteroatom-containing groups; 1, 2 wherein the method comprises oxidizing dihydrotetrazine 1 in a reaction medium in the presence of a catalyst and a stoichiometric oxidant.

First claim

What is claimed:

1. A method for catalytically converting a dihydrotetrazine 1 into a tetrazine 2, wherein one R group on the dihydrotetrazine 1 is a substituted or unsubstituted aryl, heteroaryl, alkyl, alkenyl, alkynyl, carbonyl, or heteroatom-containing group, and the other R group is selected from the group consisting of H and substituted or unsubstituted aryl, heteroaryl, alkyl, alkenyl, alkynyl, carbonyl, or heteroatom-containing groups;

wherein the method comprises oxidizing dihydrotetrazine 1 in a reaction medium in the presence of a catalyst and a stoichiometric oxidant, and
wherein the catalyst is a photocatalyst and light is utilized to activate the catalyst.

2. The method according to claim 1 , wherein the photocatalyst is one of the following compounds or a derivative thereof:

3. The method according to claim 1 , wherein the stoichiometric oxidant is at least one of O 2 , atmospheric O 2 , hydrogen peroxide, or a disulfide.

4. The method according to claim 3 , wherein the O 2 is at a concentration lower than that found under atmospheric conditions.

5. The method according to claim 1 , wherein the dihydrotetazine 1 has one of the following structures:

wherein R 1 , R 2 and R 3 are each individually selected from the group consisting of H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, carbonyl, and heteroatom-containing groups.

6. The method according to claim 5 , wherein the dihydrotetazine 1 has one of the following structures:

7. The method according to claim 1 , wherein the dihydrotetazine 1 has the following structure:

wherein R is selected from the group consisting of H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, and heteroatom-containing groups, and Ar is an aromatic or heteroaromatic group.

8. The method according to claim 7 , wherein the dihydrotetazine 1 has one of the following structures:

9. The method according to claim 1 , wherein the tetrazine 2 has one of the following structures:

Assignees

• Fox Joseph
• Jia Xinqiao
• Trout Will
• Rosenthal Joel
• Zhang Han
• Fang Yinzhi
• Thorpe Colin
• Liu Shuang
• Xie Yixin
• Univ Delaware

Inventors

• Fox Joseph
• Jia Xinqiao
• Trout Will
• Rosenthal Joel
• Zhang Han
• Fang Yinzhi
• Thorpe Colin
• Liu Shuang
• Xie Yixin

Classifications

• C07D403/14

  containing three or more hetero rings · CPC title

• C07D401/04

  directly linked by a ring-member-to-ring-member bond · CPC title

• C07D403/04

  directly linked by a ring-member-to-ring-member bond · CPC title

• C12Y111/01007

  Peroxidase (1.11.1.7), i.e. horseradish-peroxidase · CPC title

• C07D401/14 Primary

  containing three or more hetero rings · CPC title