Method for preparing 6-substituted-7-aza-indoles

1. A method of preparing 6-substituted 7-azaindoles comprising treatment of an O-methyl-N-oxide salt of 7-azaindole with a nucleophile selected from cyanide, thiocyanates, azides, phenolates, thiophenolates, alkoxides, nitrites, mercaptans, amines, cyanoacetates, phosphates, H-phosphonates and optionally substituted nitrogen-containing heterocyclic rings.

2. The method of claim 1 wherein the O-methyl-N-oxide salt of 7-azaindole is treated with aqueous cyanide.

3. The method of claim 1 wherein the O-methyl-N-oxide salt of 7-azaindole is treated with an alkoxide or a secondary amine or an optionally substituted diazole/triazole.

4. The method of claim 1 wherein the treatment is at a temperature above about RT.

5. A method of preparing 6-substituted 7-azaindoles by treatment of 7-azaindole-N-oxide m-CBA salt with alkyl-LG, followed by treatment with a nucleophile, wherein LG is a sulfonate ester.

6. A method of preparing 6-substituted 7-azaindoles by treatment of an O-methyl-N-oxide salt of 7-azaindole with a nucleophile; wherein the 6-substituted 7-azaindole is 6-(1,2,4-Triazol-1-yl)-1H-pyrrolo[2,3-b]pyridine, 6-Imidazol-1-yl-1H-pyrrolo[2,3-b]pyridine; 1-(1H-Pyrrolo[2,3-b]pyridin-6-yl)-1H-benzoimidazole; 1-(1H-Pyrrolo[2,3-b]pyridin-6-yl)-1H-benzotriazole; 6-Methoxy-1H-pyrrolo [2,3 -b] pyridine; 6-Allyloxy-1H-pyrrolo[2,3-b]pyridine; 6-Benzyloxy-1H-pyrrolo[2,3-b]pyridine; 6-(4-Morpholino)-1H-pyrrolo[2,3-b]pyridine; 6-Dodecylsulfanyl-1H-pyrrolo[2,3-b]pyridine; 6-(Naphthalene-2-ylsulfanyl)-1H-pyrrolo[2,3-b]pyridine; 6-(Dodecane-1-sulfonyl)-1H-pyrrolo[2,3-b]pyridine; 1H-Pyrrolo[2,3-b]pyridin-6-ylamine; 6-methylamino-H-pyrrolo[2,3-b]pyridine; 6-cyclopropylamino-H-pyrrolo[2,3-b]pyridine; Diethyl-(1H-pyrrolo[2,3-b]pyridin-6-yl)-amine; Allyl-(1H-pyrrolo[2,3-b]pyridin-6-yl)-amine; Pyridin-4-ylmethyl-(1H-pyrrolo[2,3-b]pyridin-6-yl)-amine; 2-(1H-Pyrrolo[2,3 -b]pyridin-6-ylamino)-propan-1-ol; 1-(1H-Pyrrolo[2,3-b]pyridin-6-ylamino)-propan-2-ol; 2-Methyl-2-(1H-pyrrolo[2,3-b]pyridin-6-ylamino)-propan-1-ol; [2-(1H-Indol-3-yl)-ethyl]-(1H-pyrrolo[2,3-b]pyridin-6-yl)-amine; Prop-2-ynyl-(1H-pyrrolo[2,3-b]pyridin-6-yl)-amine; [(S)-1-(1H-Pyrrolo[2,3-b]pyridin-6-yl)-pyrrolidin-2-yl]-MeOH; 6-Perhydro-azepin-1-yl-1H-pyrrolo[2,3-b]pyridine; or (1H-Pyrrolo[2,3-b]pyridin-6-yl)-(tetrahydro-furan-2-ylmethyl)-amine.

7. The method of claim 5 wherein alkyl-LG is dimethylsulfate.

8. The method of claim 1 wherein the O-methyl-N-oxide salt of 7-azaindole is an N-oxide-7-azaindole CBA salt.

9. The method of claim 1 where the salt is a sulfonate salt.

10. The method of claim 1 wherein the optionally substituted nitrogen-containing heterocyclic rings are an optionally substituted imidazole, pyrazole, triazole, thiadiazole, oxadiazole, indazole, benzimidazole, or benzotriazole, or their di- or tetrahydro-analogs.

11. The method of claim 1 wherein the optionally substituted nitrogen-containing heterocyclic rings are morpholine, pyrrolidine or tetrahydro-azepine.

12. The method of claim 1 wherein the alkoxide is methoxide, allyloxide or benzyloxide.

13. The method of claim 1 wherein the amines are ammonia, methylamine, cyclopropylamine, diethylamine, allylamine, pyridinylmethylamine, propanolamine, indolylethylamine, propynylamine, glycine, phenylalanine or tetrahydrofuranylmethylamine.

14. The method of claim 1 wherein the mercaptan is dodecylthiol, or naphthalenethiol.