Synthetic route to ABCD-porphyrins
A method of making a metalloporphyrin is carried out by reacting (i) a linear tetrapyrrole, said linear tetrapyrrole having a 19-acyl group and a 1-protecting group, with (ii) a metal salt under basic conditions to produce the metalloporphyrin. Products produced by such methods and intermediates useful for carrying out such methods are also described.
1. A method of making a metalloporphyrin, comprising: reacting (i) a linear tetrapyrrole, said linear tetrapyrrole having a 19-acyl group and a 1-protecting group, with (ii) a metal salt under basic conditions to produce said metalloporphyrin,
wherein said metal salt is a magnesium, zinc, copper, palladium, nickel, or indium salt.
2. The method of claim 1 , wherein said protecting group is selected from the group consisting of halo, thio, acetate, sulfonate, and triflate.
3. The method of claim 1 , wherein said metal salt is a magnesium halide.
4. The method of claim 1 , wherein said linear tetrapyrrole is selected from the group consisting of bilanes, bilins, bilenes, and biladienes.
5. The method of claim 1 , wherein said metalloporphyrin is a compound of Formula I:
and wherein said linear tetrapyrrole is a compound of Formula IIa, IIb, IIc, IId, IIe, or IIf:
wherein:
X is a protecting group selected from the group consisting of halo, thio, acetate, sulfonate, and triflate;
A, B, C, and D are each independently selected from the group consisting of: H, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkylalkenyl, cycloalkylalkynyl, heterocyclo, heterocycloalkyl, heterocycloalkenyl, heterocycloalkynyl, acetal, aryl, aryloxy, arylalkyl, arylalkenyl, arylalkynyl, heteroaryl, heteroarylalkyl, heteroarylalkenyl, heteroarylalkynyl, alkoxy, halo, mercapto, azido, cyano, acyl, formyl, carboxylic acid, acylamino, ester, amide, hydroxyl, nitro, alkylthio, amino, alkylamino, arylalkylamino, disubstituted amino, acyloxy, sulfoxyl, sulfonyl, sulfonate, sulfonic acid, sulfonamide, urea, alkoxylacylamino, aminoacyloxy, linking groups, surface attachment groups, bioconjugatable groups, targeting groups, and water soluble groups;
each R is independently selected from the group consisting of: H, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkylalkenyl, cycloalkylalkynyl, heterocyclo, heterocycloalkyl, heterocycloalkenyl, heterocycloalkynyl, acetal, aryl, aryloxy, arylalkyl, arylalkenyl, arylalkynyl, heteroaryl, heteroarylalkyl, heteroarylalkenyl, heteroarylalkynyl, alkoxy, halo, mercapto, azido, cyano, acyl, formyl, carboxylic acid, acylamino, ester, amide, hydroxyl, nitro, alkylthio, amino, alkylamino, arylalkylamino, disubstituted amino, acyloxy, sulfoxyl, sulfonyl, sulfonate, sulfonic acid, sulfonamide, urea, alkoxylacylamino, aminoacyloxy, linking groups, surface attachment groups, bioconjugatable groups, targeting groups, and water soluble groups;
or an adjacent pair of two R groups may together form an annulated arene or annulated alkene; and
M is magnesium, zinc, copper, palladium, nickel, or indium.
6. The method of claim 1 , wherein said protecting group is halo.
7. The method of claim 1 , wherein said protecting group is Br.
8. The method of claim 5 , wherein X is halo.
9. The method of claim 5 , wherein X is Br.
10. The method of claim 5 , wherein said metalloporphyrin of Formula I has the structure:
11. The method of claim 5 , wherein said linear tetrapyrrole has the structure:
where X is Br.
12. The method of claim 1 , wherein said metal salt is selected from the group consisting of metal salt is nickel (II) chloride, nickel (II) acetate, indium tribromide, and magnesium bromide.
13. The method of claim 1 , wherein said metal salt is zinc acetate.
14. The method of claim 1 , wherein said metal salt is a zinc halide.