Patent ID: 6946552

Claim:
A method of making a chlorin of Formula X: wherein: M is a metal selected from the group consisting of Cu, Zn, Mg, Pt, Pd, Sn and Al, or M is absent; K 1 , K 2 and K 4 are atoms independently selected from the group consisting of N, O, S, Se, Te, and CH; K 3 is N; S 1 , S 2 , S 3 , S 4 S 5 , S 6 , S 7 , S 8 , S 9 , S 10 , S 11 , S 12 , S 13 , and S 14 are independently selected from the group consisting of H, aryl, phenyl, cycloalkyl, alkyl, alkenyl, alkynyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido, and carbamoyl; and wherein from one to four of S 1 , S 2 , S 3 , S 4 S 5 , S 6 , S 7 , S 8 , S 9 , S 10 , S 11 , S 12 , S 13 , and S 14 may optionally be independently selected linking groups Q, wherein said linking groups Q are of the formula: wherein: n is from 0 to 10; R 3 may be present or absent; R 1 , R 2 , and R 3 are each independently selected from the group consisting of ethene, ethyne, aryl, and heteroaryl groups, which aryl and heteroaryl groups may be unsubstituted or substituted one or more times with H, aryl, phenyl, cycloalkyl, alkyl, alkenyl, alkynyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido, and carbamoyl; Y is a protected or unprotected reactive substituent selected from the group consisting of hydroxy, thio, seleno, telluro, carboxylic acid, boronic acid, phenol, silane, sulfonic acid, phosphonic acid, alkylthiol, formyl, halo, alkenyl, alkynyl, haloalkyl, alkyl phosphonate, alkyl sulfonate, alkyl carboxylate, and alkyl boronate groups; said method comprising oxidatively cyclizing a tetrahydrobilene of Formula XI: wherein Z is selected from the group consisting of halo, alkoxy, and acyloxy; in an organic solvent in the presence of a base, an oxidant and a metal salt MX n , where X is an anion, and n is 2-3, to produce a compound of Formula X above; and then optionally displacing metal M to create a free base chlorin.