Claims
- 1. A method represented by Scheme 1:
- 2. The method of claim 1, wherein X represents I.
- 3. The method of claim 1, wherein X represents Br.
- 4. The method of claim 1, wherein Z represents optionally substituted aryl.
- 5. The method of claim 1, wherein Z represents optionally substituted phenyl.
- 6. The method of claim 1, wherein the base is a carbonate, phosphate, oxide, hydroxide, alkoxide, aryloxide, amine, metal amide, fluoride, or guanidine.
- 7. The method of claim 1, wherein the base is potassium phosphate, potassium carbonate, cesium carbonate, sodium tert-butoxide, or sodium carbonate.
- 8. The method of claim 1, wherein X represents I; and Z represents optionally substituted aryl.
- 9. The method of claim 1, wherein X represents I; and Z represents optionally substituted phenyl.
- 10. The method of claim 1, wherein X represents I; Z represents optionally substituted aryl; and the base is a carbonate, phosphate, oxide, hydroxide, alkoxide, aryloxide, amine, metal amide, fluoride, or guanidine.
- 11. The method of claim 1, wherein X represents I; Z represents optionally substituted phenyl; and the base is a carbonate, phosphate, oxide, hydroxide, alkoxide, aryloxide, amine, metal amide, fluoride, or guanidine.
- 12. The method of claim 1, wherein X represents I; Z represents optionally substituted aryl; and the base is potassium phosphate, potassium carbonate, cesium carbonate, sodium tert-butoxide, or sodium carbonate.
- 13. The method of claim 1, wherein X represents I; Z represents optionally substituted phenyl; and the base is potassium phosphate, potassium carbonate, cesium carbonate, sodium tert-butoxide, or sodium carbonate.
- 14. The method of claim 1, wherein X represents Br; and Z represents optionally substituted aryl.
- 15. The method of claim 1, wherein X represents Br; and Z represents optionally substituted phenyl.
- 16. The method of claim 1, wherein X represents Br; Z represents optionally substituted aryl; and the base is a carbonate, phosphate, oxide, hydroxide, alkoxide, aryloxide, amine, metal amide, fluoride, or guanidine.
- 17. The method of claim 1, wherein X represents Br; Z represents optionally substituted phenyl; and the base is a carbonate, phosphate, oxide, hydroxide, alkoxide, aryloxide, amine, metal amide, fluoride, or guanidine.
- 18. The method of claim 1, wherein X represents Br; Z represents optionally substituted aryl; and the base is potassium phosphate, potassium carbonate, cesium carbonate, sodium tert-butoxide, or sodium carbonate.
- 19. The method of claim 1, wherein X represents Br; Z represents optionally substituted phenyl; and the base is potassium phosphate, potassium carbonate, cesium carbonate, sodium tert-butoxide, or sodium carbonate.
- 20. The method of any of claims 1-19, wherein the catalyst is present in less than or equal to about 10 mol % relative to Z—X.
- 21. The method of any of claims 1-19, wherein the catalyst is present in less than or equal to about 5 mol % relative to Z—X.
- 22. The method of any of claims 1-19, wherein the method is conducted at a temperature less than about 150 C.
- 23. The method of any of claims 1-19, wherein the method is conducted at a temperature less than about 100 C.
- 24. The method of any of claims 1-19, wherein the method is conducted at a temperature less than about 90 C.
- 25. The method of any of claims 1-19, wherein the method is conducted at a temperature less than about 85 C.
- 26. A method represented by Scheme 2:
- 27. The method of claim 26, wherein M represents a sodium cation, potassium cation or copper cation.
- 28. The method of claim 26, wherein X represents Br.
- 29. The method of claim 26, wherein Y represents I.
- 30. The method of claim 26, wherein the ligand comprised by the catalyst is an optionally substituted diamine.
- 31. The method of claim 26, wherein the ligand comprised by the catalyst is an optionally substituted 1,2-diaminocyclohexane, 1,2-diaminoalkane, 1,3-diaminoalkane, or 1,10-phenanthroline.
- 32. The method of claim 26, wherein the ligand comprised by the catalyst is an optionally substituted 1,2-diaminocyclohexane, 1,2-diaminoethane, 1,3-diaminopropane, or 1,10-phenanthroline.
- 33. The method of claim 26, wherein the ligand comprised by the catalyst is cis-1,2-diaminocyclohexane, trans-1,2-diaminocyclohexane, a mixture of cis- and trans-1,2-diaminocyclohexane, cis-N,N′-dimethyl-1,2-diaminocyclohexane, trans-N,N′-dimethyl-1,2-diaminocyclohexane, a mixture of cis- and trans-N,N′-dimethyl-1,2-diaminocyclohexane, cis-N-tolyl-1,2-diaminocyclohexane, trans-N-tolyl-1,2-diaminocyclohexane, or a mixture of cis- and trans-N-tolyl-1,2-diaminocyclohexane.
- 34. The method of claim 26, wherein the ligand comprised by the catalyst is trans-N,N′-dimethyl-1,2-diaminocyclohexane or N,N′-dimethylethylenediamine.
- 35. The method of claim 26, wherein M represents a sodium cation, potassium cation or copper cation; and X represents Br.
- 36. The method of claim 26, wherein M represents a sodium cation, potassium cation or copper cation; X represents Br; and Y represents I.
- 37. The method of claim 26, wherein M represents a sodium cation, potassium cation or copper cation; X represents Br; Y represents I; and the ligand comprised by the catalyst is an optionally substituted diamine.
- 38. The method of claim 26, wherein M represents a sodium cation, potassium cation or copper cation; X represents Br; Y represents I; and the ligand comprised by the catalyst is an optionally substituted 1,2-diaminocyclohexane, 1,2-diaminoalkane, 1,3-diaminoalkane, or 1,10-phenanthroline.
- 39. The method of claim 26, wherein M represents a sodium cation, potassium cation or copper cation; X represents Br; Y represents I; and the ligand comprised by the catalyst is an optionally substituted 1,2-diaminocyclohexane, 1,2-diaminoethane, 1,3-diaminopropane, or 1,10-phenanthroline.
- 40. The method of claim 26, wherein M represents a sodium cation, potassium cation or copper cation; X represents Br; Y represents I; and the ligand comprised by the catalyst is cis-1,2-diaminocyclohexane, trans-1,2-diaminocyclohexane, a mixture of cis- and trans-1,2-diaminocyclohexane, cis-N,N′-dimethyl-1,2-diaminocyclohexane, trans-N,N′-dimethyl-1,2-diaminocyclohexane, a mixture of cis- and trans-N,N′-dimethyl-1,2-diaminocyclohexane, cis-N-tolyl-1,2-diaminocyclohexane, trans-N-tolyl-1,2-diaminocyclohexane, or a mixture of cis- and trans-N-tolyl-1,2-diaminocyclohexane.
- 41. The method of claim 26, wherein M represents a sodium cation, potassium cation or copper cation; X represents Br; Y represents I; and the ligand comprised by the catalyst is trans-N,N′-dimethyl-1,2-diaminocyclohexane or N,N′-dimethylethylenediamine.
- 42. The method of any of claims 26-41, wherein the catalyst is present in less than or equal to about 10 mol % relative to Z—X.
- 43. The method of any of claims 26-41, wherein the catalyst is present in less than or equal to about 5 mol % relative to Z—X.
- 44. The method of any of claims 26-41, wherein the method is conducted at a temperature less than about 150 C.
- 45. The method of any of claims 26-41, wherein the method is conducted at a temperature less than about 140 C.
- 46. The method of any of claims 26-41, wherein the method is conducted at a temperature less than about 125 C.
- 47. The method of any of claims 26-41, wherein the method is conducted at a temperature less than about 115 C.
- 48. A method represented by Scheme 3:
- 49. The method of claim 48, wherein M represents a sodium cation, potassium cation or copper cation.
- 50. The method of claim 48, wherein the ligand comprised by the catalyst is an optionally substituted diamine.
- 51. The method of claim 48, wherein the ligand comprised by the catalyst is an optionally substituted 1,2-diaminocyclohexane, 1,2-diaminoalkane, 1,3-diaminoalkane, or 1,10-phenanthroline.
- 52. The method of claim 48, wherein the ligand comprised by the catalyst is an optionally substituted 1,2-diaminocyclohexane, 1,2-diaminoethane, 1,3-diaminopropane, or 1,10-phenanthroline.
- 53. The method of claim 48, wherein the ligand comprised by the catalyst is cis-1,2-diaminocyclohexane, trans-1,2-diaminocyclohexane, a mixture of cis- and trans-1,2-diaminocyclohexane, cis-N,N′-dimethyl-1,2-diaminocyclohexane, trans-N,N′-dimethyl-1,2-diaminocyclohexane, a mixture of cis- and trans-N,N′-dimethyl-1,2-diaminocyclohexane, cis-N-tolyl-1,2-diaminocyclohexane, trans-N-tolyl-1,2-diaminocyclohexane, or a mixture of cis- and trans-N-tolyl-1,2-diaminocyclohexane.
- 54. The method of claim 48, wherein the ligand comprised by the catalyst is trans-N,N′-dimethyl-1,2-diaminocyclohexane or N,N′-dimethylethylenediamine.
- 55. The method of claim 48, wherein M represents a sodium cation, potassium cation or copper cation; and the ligand comprised by the catalyst is an optionally substituted diamine.
- 56. The method of claim 48, wherein M represents a sodium cation, potassium cation or copper cation; and the ligand comprised by the catalyst is an optionally substituted 1,2-diaminocyclohexane, 1,2-diaminoalkane, 1,3-diaminoalkane, or 1,10-phenanthroline.
- 57. The method of claim 48, wherein M represents a sodium cation, potassium cation or copper cation; and the ligand comprised by the catalyst is an optionally substituted 1,2-diaminocyclohexane, 1,2-diaminoethane, 1,3-diaminopropane, or 1,10-phenanthroline.
- 58. The method of claim 48, wherein M represents a sodium cation, potassium cation or copper cation; and the ligand comprised by the catalyst is cis-1,2-diaminocyclohexane, trans-1,2-diaminocyclohexane, a mixture of cis- and trans-1,2-diaminocyclohexane, cis-N,N′-dimethyl-1,2-diaminocyclohexane, trans-N,N′-dimethyl-1,2-diaminocyclohexane, a mixture of cis- and trans-N,N′-dimethyl-1,2-diaminocyclohexane, cis-N-tolyl-1,2-diaminocyclohexane, trans-N-tolyl-1,2-diaminocyclohexane, or a mixture of cis- and trans-N-tolyl-1,2-diaminocyclohexane.
- 59. The method of claim 48, wherein M represents a sodium cation, potassium cation or copper cation; and the ligand comprised by the catalyst is trans-N,N′-dimethyl-1,2-diaminocyclohexane or N,N′-dimethylethylenediamine.
- 60. The method of any of claims 48-59, wherein the catalyst is present in less than or equal to about 15 mol % relative to Z—I.
- 61. The method of any of claims 48-59, wherein the catalyst is present in less than or equal to about 10 mol % relative to Z—I.
- 62. The method of any of claims 48-59, wherein the catalyst is present in less than or equal to about 5 mol % relative to Z—I.
- 63. The method of any of claims 48-59, wherein the method is conducted at a temperature less than about 150 C.
- 64. The method of any of claims 48-59, wherein the method is conducted at a temperature less than about 140 C.
- 65. The method of any of claims 48-59, wherein the method is conducted at a temperature less than about 125 C.
- 66. The method of any of claims 48-59, wherein the method is conducted at a temperature less than about 115 C.
- 67. A method represented by Scheme 4:
- 68. The method of claim 67, wherein M represents independently for each occurrence a sodium cation, potassium cation or copper cation.
- 69. The method of claim 67, wherein X represents Br.
- 70. The method of claim 67, wherein the ligand comprised by the catalyst is an optionally substituted diamine.
- 71. The method of claim 67, wherein the ligand comprised by the catalyst is an optionally substituted 1,2-diaminocyclohexane, 1,2-diaminoalkane, 1,3-diaminoalkane, or 1,10-phenanthroline.
- 72. The method of claim 67, wherein the ligand comprised by the catalyst is an optionally substituted 1,2-diaminocyclohexane, 1,2-diaminoethane, 1,3-diaminopropane, or 1,10-phenanthroline.
- 73. The method of claim 67, wherein the ligand comprised by the catalyst is cis-1,2-diaminocyclohexane, trans-1,2-diaminocyclohexane, a mixture of cis- and trans-1,2-diaminocyclohexane, cis-N,N′-dimethyl-1,2-diaminocyclohexane, trans-N,N′-dimethyl-1,2-diaminocyclohexane, a mixture of cis- and trans-N,N′-dimethyl-1,2-diaminocyclohexane, cis-N-tolyl-1,2-diaminocyclohexane, trans-N-tolyl-1,2-diaminocyclohexane, or a mixture of cis- and trans-N-tolyl-1,2-diaminocyclohexane.
- 74. The method of claim 67, wherein the ligand comprised by the catalyst is trans-N,N′-dimethyl-1,2-diaminocyclohexane or N,N′-dimethylethylenediamine.
- 75. The method of claim 67, wherein M represents independently for each occurrence a sodium cation, potassium cation or copper cation; and X represents Br.
- 76. The method of claim 67, wherein M represents independently for each occurrence a sodium cation, potassium cation or copper cation; X represents Br; and the ligand comprised by the catalyst is an optionally substituted diamine.
- 77. The method of claim 67, wherein M represents independently for each occurrence a sodium cation, potassium cation or copper cation; X represents Br; and the ligand comprised by the catalyst is an optionally substituted 1,2-diaminocyclohexane, 1,2-diaminoalkane, 1,3-diaminoalkane, or 1,10-phenanthroline.
- 78. The method of claim 67, wherein M represents independently for each occurrence a sodium cation, potassium cation or copper cation; X represents Br; and the ligand comprised by the catalyst is an optionally substituted 1,2-diaminocyclohexane, 1,2-diaminoethane, 1,3-diaminopropane, or 1,10-phenanthroline.
- 79. The method of claim 67, wherein M represents independently for each occurrence a sodium cation, potassium cation or copper cation; X represents Br; and the ligand comprised by the catalyst is cis-1,2-diaminocyclohexane, trans-1,2-diaminocyclohexane, a mixture of cis- and trans-1,2-diaminocyclohexane, cis-N,N′-dimethyl-1,2-diaminocyclohexane, trans-N,N′-dimethyl-1,2-diaminocyclohexane, a mixture of cis- and trans-N,N′-dimethyl-1,2-diaminocyclohexane, cis-N-tolyl-1,2-diaminocyclohexane, trans-N-tolyl-1,2-diaminocyclohexane, or a mixture of cis- and trans-N-tolyl-1,2-diaminocyclohexane.
- 80. The method of claim 67, wherein M represents independently for each occurrence a sodium cation, potassium cation or copper cation; X represents Br; and the ligand comprised by the catalyst is trans-N,N′-dimethyl-1,2-diaminocyclohexane or N,N′-dimethylethylenediamine.
- 81. The method of any of claims 67-80, wherein the catalyst is present in less than or equal to about 15 mol % relative to Z—X.
- 82. The method of any of claims 67-80, wherein the catalyst is present in less than or equal to about 10 mol % relative to Z—X.
- 83. The method of any of claims 67-80, wherein the catalyst is present in less than or equal to about 5 mol % relative to Z—X.
- 84. The method of any of claims 67-80, wherein the method is conducted at a temperature less than about 150 C.
- 85. The method of any of claims 67-80, wherein the method is conducted at a temperature less than about 140 C.
- 86. The method of any of claims 67-80, wherein the method is conducted at a temperature less than about 125 C.
- 87. The method of any of claims 67-80, wherein the method is conducted at a temperature less than about 115 C.
RELATED APPLICATIONS
[0001] This application claims the benefit of priority to U.S. Provisional Application serial No. 60/400,902, filed Aug. 2, 2002; the entirety of which is hereby incorporated by reference.
GOVERNMENT SUPPORT
[0002] This invention was made with support from the National Institutes of Health (grant number RO1-GM58160); therefore, the government has certain rights in the invention.
Provisional Applications (1)
|
Number |
Date |
Country |
|
60400902 |
Aug 2002 |
US |