IP Library › Granted Patent US 7,956,193
Granted Patent B2
US 7,956,193 · App. 12/151,182 · Granted Jun 7, 2011

Intramolecular C-H amination with sulfonyl azides

Assignee: University of South Florida
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Quick Facts
Patent No.
US 7,956,193
App. No.
12/151,182
Granted
Jun 7, 2011
Kind
B2
Abstract

Cobalt (II) complexes of porphyrins are effective catalysts for intramolecular nitrene insertion of C—H bonds with arylsulfonyl azides. The cobalt-catalyzed process can proceed efficiently under mild and neutral conditions in low catalyst loading without the need of other reagents or additives, generating nitrogen gas as the only byproduct. Using the simple tetraphenylporphyrin (TPP) as the ligand, the cobalt-catalyzed intramolecular amidation can be applied to primary, secondary, and tertiary C—H bonds and suitable for a broad range of arylsulfonyl azides, leading to the syntheses of various benzosultam derivatives in excellent yields

Claims (36)

1. A process for the preparation of a sultam, the process comprising treating a sulfonylazide with an asymmetric cobalt (II) porphyrin complex to catalyze the amination of a C—H bond to form the sultam, the sulfonylazide corresponding to Formula 9a and the sultam corresponding to Formula 9

wherein

R 1 and R 2 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, halo, hydroxyl, alkoxyl, or heterocyclo,

each R 7 is independently hydrocarbyl, substituted hydrocarbyl, halo, nitro, alkoxyl, hydroxyl, acyl, acyloxy, or heterocyclo, and

m is 0 to 4.

2. The process of claim 1 wherein m is 1 to 4 and each R 7 is independently alkyl, halo, alkoxyl, hydroxyl, or nitro.

3. The process of claim 1 wherein m is 1 to 4 and each R 7 is independently alkyl, substituted alkyl, halo or nitro.

4. The process of claim 1 wherein m is 1 to 4 and each R 7 is independently alkyl.

5. The process of claim 1 wherein one of R 1 and R 2 is hydrogen and the other is hydrocarbyl, substituted hydrocarbyl, halo, hydroxyl, alkoxyl, or heterocyclo.

6. The process of claim 1 wherein R l is hydrogen and R 2 is alkyl, aryl, or heterocyclo.

7. The process of claim 1 wherein m is 1 to 4, each R 7 is independently alkyl, halo, alkoxyl, hydroxyl, or nitro, and R 1 and R 2 are hydrogen.

8. The process of claim 1 wherein m is 1 to 4, each R 7 is independently alkyl, halo, alkoxyl, hydroxyl, or nitro, one of R 1 and R 2 is hydrogen, and the other of R 1 and R 2 is hydrocarbyl, substituted hydrocarbyl, halo, hydroxyl, alkoxyl, or heterocyclo.

9. The process of claim 1 wherein the metal porphyrin complex is a metal porphyrin complex corresponding to Formula Co(3,5-ditBuChenPhyrin), Formula Co(2,6-diMeORuppelPhyrin), Formula Co(2,6-diMeOZhuPhyrin), Formula Co(Por1), Formula Co(Por2), Formula Co(Cor1)PPh 3 , Formula Co(Cor2)PPh 3 or Formula Co(Cor1)PPh 3 :

10. The process of claim 2 wherein the metal porphyrin complex is a metal porphyrin complex corresponding to Formula Co(3,5-ditBuChenPhyrin), Formula Co(2,6-diMeORuppelPhyrin), Formula Co(2,6-diMeOZhuPhyrin), Formula Co(Por1), Formula Co(Por2), Formula Co(Cor1)PPh 3 , Formula Co(Cor2)PPh 3 or Formula Co(Cor1)PPh 3 :

11. The process of claim 3 wherein the metal porphyrin complex is a metal porphyrin complex corresponding to Formula Co(3,5-ditBuChenPhyrin), Formula Co(2,6-diMeORuppelPhyrin), Formula Co(2,6-diMeOZhuPhyrin), Formula Co(Por1), Formula Co(Por2), Formula Co(Cor1)PPh 3 , Formula Co(Cor2)PPh 3 or Formula Co(Cor1)PPh 3 :

12. The process of claim 4 wherein the metal porphyrin complex is a metal porphyrin complex corresponding to Formula Co(3,5-ditBuChenPhyrin), Formula Co(2,6-diMeORuppelPhyrin), Formula Co(2,6-diMeOZhuPhyrin), Formula Co(Por1), Formula Co(Por2), Formula Co(Cor1)PPh 3 , Formula Co(Cor2)PPh 3 or Formula Co(Cor1)PPh 3 :

13. The process of claim 5 wherein the metal porphyrin complex is a metal porphyrin complex corresponding to Formula Co(3,5-ditBuChenPhyrin), Formula Co(2,6-diMeORuppelPhyrin), Formula Co(2,6-diMeOZhuPhyrin), Formula Co(Por1), Formula Co(Por2), Formula Co(Cor1)PPh 3 , Formula Co(Cor2)PPh 3 or Formula Co(Cor1)PPh 3 :

14. The process of claim 6 wherein the metal porphyrin complex is a metal porphyrin complex corresponding to Formula Co(3,5-ditBuChenPhyrin), Formula Co(2,6-diMeORuppelPhyrin), Formula Co(2,6-diMeOZhuPhyrin), Formula Co(Por1), Formula Co(Por2), Formula Co(Cor1)PPh 3 , Formula Co(Cor2)PPh 3 or Formula Co(Cor1)PPh 3 :

15. The process of claim 7 wherein the metal porphyrin complex is a metal porphyrin complex corresponding to Formula Co(3,5-ditBuChenPhyrin), Formula Co(2,6-diMeORuppelPhyrin), Formula Co(2,6-diMeOZhuPhyrin), Formula Co(Por1), Formula Co(Por2), Formula Co(Cor1)PPh 3 , Formula Co(Cor2)PPh 3 or Formula Co(Cor1)PPh 3 :

16. The process of claim 8 wherein the metal porphyrin complex is a metal porphyrin complex corresponding to Formula Co(3,5-ditBuChenPhyrin), Formula Co(2,6-diMeORuppelPhyrin), Formula Co(2,6-diMeOZhuPhyrin), Formula Co(Por1), Formula Co(Por2), Formula Co(Cor1)PPh 3 , Formula Co(Cor2)PPh 3 or Formula Co(Cor1)PPh 3 :

17. The process of claim 1 wherein the metal porphyrin complex is

18. The process of claim 2 wherein the metal porphyrin complex is

19. The process of claim 3 wherein the metal porphyrin complex is

20. The process of claim 4 wherein the metal porphyrin complex is

21. The process of claim 5 wherein the metal porphyrin complex is

22. The process of claim 6 wherein the metal porphyrin complex is

23. The process of claim 7 wherein the metal porphyrin complex is

24. The process of claim 8 wherein the metal porphyrin complex is

25. The process of claim 11 wherein the metal porphyrin complex is

26. The process of claim 2 wherein the metal porphyrin complex is

27. The process of claim 3 wherein the metal porphyrin complex is

28. The process of claim 4 wherein the metal porphyrin complex is

29. The process of claim 5 wherein the metal porphyrin complex is

30. The process of claim 6 wherein the metal porphyrin complex is

31. The process of claim 7 wherein the metal porphyrin complex is

32. The process of claim 8 wherein the metal porphyrin complex is

Assignments (3)
CONFIRMATORY LICENSE Recorded Aug 12, 2011
From: UNIVERSITY OF SOUTH FLORIDA
To: NATIONAL SCIENCE FOUNDATION
Reel/Frame 026744/0763 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 12, 2009
From: ZHANG, X. PETER
To: UNIVERSITY OF SOUTH FLORIDA OF TAMPA, FLORIDA
Reel/Frame 022247/0972 →
CONFIRMATORY LICENSE Recorded Sep 30, 2008
From: FLORIDA, UNIVERSITY OF SOUTH
To: FOUNDATION, NATIONAL SCIENCE
Reel/Frame 021607/0172 →
Continuity (2)
Provisional Application 60916071 · May 4, 2007
Related Publication 20100063277A1 · Mar 11, 2010