Claims
- 1. A dirhodium catalyst composition comprising:
a dirhodium catalyst which comprises a Rh—Rh moiety and four bridging ligand moieties; and a solid support, wherein said dirhodium catalyst and said solid support are bound together and wherein said dirhodium catalyst and said solid support are not covalently bound together via one or more of said bridging ligand moieties.
- 2. A composition according to claim 1, wherein each of the four ligand moieties are independently selected from carboxylate moieties and amide moieties.
- 3. A composition according to claim 1, wherein said dirhodium catalyst is a dirhodium tetracarboxylate catalyst.
- 4. A composition according to claim 1, wherein said dirhodium catalyst is a dirhodium tetracarboxamidate catalyst.
- 5. A composition according to claim 1, wherein said solid support is a macroporous solid support.
- 6. A composition according to claim 1, wherein said solid support is a cross-linked polystyrene resin.
- 7. A composition according to claim 1, wherein said solid support is a macroporous cross-linked polystyrene resin.
- 8. A composition according to claim 1, wherein said solid support is a cross-linked polystyrene resin and wherein the cross-linked polystyrene resin is more highly cross-linked than a 1% cross-linked polystyrene resin.
- 9. A composition according to claim 1, wherein said solid support is a cross-linked polystyrene resin comprising pendant groups having the formula:
- 10. A composition according to claim 9, wherein W represents a hydroxyl group, a halogen, or an alkoxy group.
- 11. A composition according to claim 9, wherein W represents an alkoxy group.
- 12. A composition according to claim 9, wherein W represents a —OW′ group and wherein W′ is an aryl group.
- 13. A composition according to claim 9, wherein W represents a —OW′ group and wherein W′ is a substituted or unsubstituted phenyl group or a substituted or unsubstituted pyridyl group.
- 14. A composition according to claim 9, wherein W represents a —OW′ group and wherein W′ is a phenyl group or 4-pyridyl group.
- 15. A composition according to claim 9, wherein W represents a —OW′ group and wherein W′ is nitrogen-containing heterocycle.
- 16. A composition according to claim 15, wherein the nitrogen-containing heterocycle is a pyridyl group, a quinolinyl group, an isoquinolinyl group, an imidazolyl group, or a benzimidazolyl group.
- 17. A composition according to claim 1, wherein said solid support is a cross-linked polystyrene resin comprising pendant groups having the formula:
- 18. A composition according to claim 1, wherein said solid support comprises a nitrogen-containing heterocyclic pendant group.
- 19. A composition according to claim 18, wherein the nitrogen-containing heterocyclic pendant group is a pyridyl group, a quinolinyl group, an isoquinolinyl group, an imidazolyl group, or a benzimidazolyl group.
- 20. A composition according to claim 1, wherein said solid support comprises a nitrogen-containing heterocyclic pendant group and wherein said dirhodium catalyst and said solid support are bound together via a bond between at least one of the rhodiums' axial positions and the heterocyclic pendant group's nitrogen.
- 21. A composition according to claim 1, wherein said solid support comprises a pendant substituted or unsubstituted phenyl group.
- 22. A composition according to claim 1, wherein said dirhodium catalyst is a chiral dirhodium catalyst.
- 23. A composition according to claim 1, wherein said dirhodium catalyst is a chiral dirhodium tetracarboxylate catalyst.
- 24. A composition according to claim 1, wherein said dirhodium catalyst is a chiral dirhodium tetracarboxamidate catalyst.
- 25. A composition according to claim 1, wherein said dirhodium catalyst has the formula:
- 26. A composition according to claim 25, wherein Z4 has the formula —CH2CH2CH2—.
- 27. A composition according to claim 25, wherein said dirhodium tetracarboxylate catalyst has one of the following formulae:
- 28. A composition according to claim 25, wherein said dirhodium tetracarboxylate catalyst has D2 symmetry.
- 29. A composition according to claim 1, wherein said dirhodium catalyst is a dirhodium tetracarboxylate catalyst having the formula:
- 30. A composition according to claim 29, wherein said dirhodium tetracarboxylate catalyst has the formula:
- 31. A composition according to claim 29, wherein Z2 and Z3 each have the formula —CH2CH2—.
- 32. A composition according to claim 29, wherein Z1 is a 1,3-phenylene moiety.
- 33. A composition according to claim 29, wherein said dirhodium tetracarboxylate catalyst has one of the following formulae:
- 34. A composition according to claim 29, wherein said dirhodium tetracarboxylate catalyst has one of the following formulae:
- 35. A composition according to claim 1, wherein said dirhodium catalyst has the following formula:
- 36. A dirhodium catalyst composition comprising:
a dirhodium tetracarboxylate catalyst; and a solid support, wherein said dirhodium tetracarboxylate catalyst and said solid support are bound together.
- 37. A dirhodium catalyst composition according to claim 36, wherein said dirhodium tetracarboxylate catalyst has the formula:
- 38. A dirhodium catalyst composition according to claim 36, wherein said dirhodium tetracarboxylate catalyst has the formula:
- 39. A dirhodium catalyst composition according to claim 36, wherein said dirhodium tetracarboxylate catalyst is a chiral dirhodium tetracarboxylate catalyst.
- 40. A dirhodium catalyst composition comprising:
a dirhodium catalyst comprising a Rh—Rh moiety; and a solid support, wherein said dirhodium catalyst and said solid support are bound together via at least one of the rhodiums' axial positions.
- 41. A composition according to claim 40, wherein the solid support comprises a nitrogen-containing heterocyclic pendant group and wherein said dirhodium catalyst and said solid support are bound together via a bond between at least one of the rhodiums' axial positions and the heterocyclic pendant group's nitrogen.
- 42. A composition according to claim 41, wherein the nitrogen-containing heterocyclic pendant group is a pyridyl group, a quinolinyl group, an isoquinolinyl group, an imidazolyl group, or a benzimidazolyl group.
- 43. A method for making a dirhodium catalyst composition according to claim 1, said method comprising:
providing a dirhodium catalyst which comprises a Rh—Rh moiety and four bridging ligand moieties; and contacting the dirhodium catalyst with a solid support under conditions effective to bind the dirhodium catalyst and the solid support together and to produce the dirhodium catalyst composition.
- 44. A method according to claim 43, wherein each of the four bridging ligand moieties are independently selected from carboxylate moieties and amide moieties.
- 45. A method according to claim 43, wherein the dirhodium catalyst is a dirhodium tetracarboxylate catalyst.
- 46. A method according to claim 43, wherein the dirhodium catalyst is a dirhodium tetracarboxamidate catalyst.
- 47. A method according to claim 43, wherein the dirhodium catalyst is a chiral dirhodium catalyst.
- 48. A method according to claim 43, wherein the dirhodium catalyst has the formula:
- 49. A method according to claim 48, wherein Z4 has the formula —CH2CH2CH2—.
- 50. A method according to claim 48, wherein the dirhodium tetracarboxylate catalyst has one of the following formulae:
- 51. A method according to claim 48, wherein the dirhodium tetracarboxylate catalyst has D2 symmetry.
- 52. A method according to claim 43, wherein the dirhodium tetracarboxylate catalyst has the formula:
- 53. A method according to claim 52, wherein the dirhodium tetracarboxylate catalyst has the formula:
- 54. A method according to claim 52, wherein Z2 and Z3 each have the formula —CH2CH2—.
- 55. A method according to claim 52, wherein Z1 is a 1,3-phenylene moiety.
- 56. A method according to claim 52, wherein the dirhodium tetracarboxylate catalyst has one of the following formulae:
- 57. A method according to claim 52, wherein the dirhodium tetracarboxylate catalyst has one of the following formulae:
- 58. A method according to claim 43, wherein the solid support comprises a nitrogen-containing heterocyclic pendant group.
- 59. A method according to claim 58, wherein the nitrogen containing heterocyclic pendant group is a pyridyl group, a quinolinyl group, an isoquinolinyl group, an imidazolyl group, or a benzimidazolyl group.
- 60. A method according to claim 43, wherein the solid support comprises a nitrogen-containing heterocyclic pendant group and wherein the dirhodium catalyst and the solid support are bound together via a bond between at least one of the rhodiums' axial positions and the heterocyclic pendant group's nitrogen.
- 61. A method according to claim 43, wherein the solid support comprises a pendant substituted or unsubstituted phenyl group.
- 62. A method for making a dirhodium catalyst composition according to claim 36, said method comprising:
providing a dirhodium tetracarboxylate catalyst; and contacting the dirhodium tetracarboxylate catalyst with a solid support under conditions effective to bind the dirhodium tetracarboxylate catalyst and the solid support together and to produce the dirhodium catalyst composition.
- 63. A method according to claim 62, wherein the dirhodium tetracarboxylate catalyst has the formula:
- 64. A method according to claim 62, wherein the dirhodium tetracarboxylate catalyst has the formula:
- 65. A method according to claim 62, wherein said dirhodium tetracarboxylate catalyst is a chiral dirhodium tetracarboxylate catalyst.
- 66. A method for making a dirhodium catalyst composition according to claim 40, said method comprising:
providing a dirhodium catalyst comprising a Rh—Rh moiety; and contacting the dirhodium catalyst with a solid support under conditions effective to bind the dirhodium catalyst and the solid support together via at least one of the rhodiums' axial positions and to produce the dirhodium catalyst composition.
- 67. A method according to claim 66, wherein the solid support comprises a nitrogen-containing heterocyclic pendant group and wherein the dirhodium catalyst and the solid support are bound together via a bond between at least one of the rhodiums' axial positions and the heterocyclic pendant group's nitrogen.
- 68. A composition according to claim 67, wherein the nitrogen-containing heterocyclic pendant group is a pyridyl group, a quinolinyl group, an isoquinolinyl group, an imidazolyl group, or a benzimidazolyl group.
- 69. A method of producing a compound having the following formula (CI):
- 70. A method according to claim 69, wherein R1 and R3, together with the atoms to which they are bonded, form a phenyl ring.
- 71. A method according to claim 69, wherein the compound of formula (CI) has the following formula (CIII):
- 72. A method according to claim 71, wherein X is NH, Y is CO2R12, R12 is a methyl group, n is 4, and R1 and R3, together with the atoms to which they are bonded, form a phenyl ring.
- 73. A method according to claim 71, wherein the compound of formula (CIII) has the formula:
- 74. A method according to claim 73, wherein X is NH, Y is CO2R12, R12 is a methyl group, n is 4, and R1 and R3, together with the atoms to which they are bonded, form a phenyl ring.
- 75. A method according to claim 69, wherein X is NR11 and R31 and R32, taken together with the atoms to which they are bonded, form a ring having the formula:
- 76. A method according to claim 75, wherein the compound has the formula:
- 77. A method of catalyzing an aryldiazomethane or a vinyldiazomethane insertion reaction, said method comprising:
providing a aryldiazomethane or a vinyldiazomethane; providing a dirhodium catalyst composition according to claim 1; and contacting the aryldiazomethane or the vinyldiazomethane with the dirhodium catalyst composition under conditions effective to catalyze the aryldiazomethane or vinyldiazomethane insertion reaction.
- 78. A compound produced by a method according to claim 77.
- 79. A compound containing a C—H bond, wherein said C—H bond is produced using a method according to claim 77.
- 80. A method of producing a compound having the following formula (CIV):
- 81. A method according to claim 80, wherein the compound of formula (CIV) has the following formula (CV):
- 82. A method for preparing a cyclopentene, said method comprising:
providing a compound of formula (CV) in accordance with a method of claim 81 in which at least one of R1 and R2 is H and in which R132 is an electron donating group; and converting the compound of formula (CV) to the cyclopentene.
- 83. A method according to claim 82, wherein said converting is carried out in the presence of a Lewis acid.
- 84. A method for preparing a dihydrofuran, said method comprising:
providing a compound of formula (CV) in accordance with a method of claim 81 in which at least one of R1 and R2 is H, in which R132 is an electron donating group, and in which R3 is a silyloxy group; and converting the compound of formula (CV) to the dihydrofuran.
- 85. A method according to claim 84, wherein said converting is carried out in the presence of a fluoride.
- 86. A method for preparing a butenolide, said method comprising:
providing a compound of formula (CV) in accordance with a method of claim 81 in which at least one of R1 and R2 is H, in which R132 is an electron donating group, in which Y is a carboxylic acid ester of the formula —COOR1601, and in which R160 is a tertiary alkyl moiety; and converting the compound of formula (CV) to the butenolide.
- 87. A method according to claim 86, wherein said converting is carried out in the presence of Lewis acid catalyst.
- 88. A method of producing a compound having the following formula (CVII):
- 89. A method according to claim 88, wherein R2 is H; R1 and R3, together with the atoms to which they are bonded, form a phenyl ring; R132 is H; R133 is a 4-alkoxyphenyl group; R134 is a phenyl group; Y is a carboxylic acid ester; and Y′ is an aldehyde group, a hydroxymethyl group, a vinyl group, or an ethyl group.
- 90. A method of producing a compound having the following formula (CVIII):
- 91. A method of producing a compound having the following formula (CIX):
- 92. A method of producing a compound having the following formula (CX):
- 93. A method of catalyzing an aryldiazomethane or a vinyldiazomethane cyclopropanation reaction, said method comprising:
providing a aryldiazomethane or a vinyldiazomethane; providing a dirhodium catalyst composition according to claim 1; and contacting the aryldiazomethane or the vinyldiazomethane with the dirhodium catalyst composition under conditions effective to catalyze the aryldiazomethane or vinyldiazomethane cyclopropanation reaction.
- 94. A compound produced by a method according to claim 93.
- 95. A compound containing a C—C bond, wherein said C—C bond is produced using a method according to claim 93.
- 96. A method of producing optionally substituted cycloheptadienes or optionally substituted bicyclooctadienes, said method comprising:
providing a diazo compound having the formula: 131where R1, R2, and R3 are independently selected from H, alkyl, aryl, silyloxy, or vinyl or where R1 and R3, together with the atoms to which they are bonded, form a 5-12 membered ring; where Y is an electron withdrawing group; and converting the diazo compound with a optionally substituted homocyclic, heterocyclic, or non-cyclic diene in the presence of a dirhodium catalyst composition according to claim 1 under conditions effective to produce the compound.
- 97. A method according to claim 96, wherein the optionally substituted homocyclic, heterocyclic, or non-cyclic diene has the formula:
- 98. A method according to claim 97, wherein R143 and R145 together represent a substituted or unsubstituted bivalent amino moiety having the formula —N(R150)— in which R150 is H, an aryl group, or alkyl group.
- 99. A method for producing a 3-aryltropane, said method comprising:
providing a compound of formula (CXI) in accordance with a method of claim 98; and converting the compound having formula (CXI) to a 3-aryltropane using an aryl Grignard reagent.
- 100. A method according to claim 99, wherein the 3-aryltropane has the formula:
- 101. A method of catalyzing a [3+4] annulation reaction, said method comprising:
providing a vinyldiazomethane; providing a dirhodium catalyst composition according to claim 1; and contacting the vinyldiazomethane with the dirhodium catalyst composition under conditions effective to produce a seven or eight membered ring or ring system.
- 102. A compound containing a seven or eight membered ring or ring system produced by a method according to claim 101.
- 103. A compound containing a seven or eight membered ring or ring system, wherein said seven or eight membered ring or ring system is produced using a method according to claim 101.
- 104. A method for producing a compound having the following formula (CXII):
- 105. A method for making a compound having the following formula (CXIII):
- 106. A method according to claim 105, wherein R1 and R3, together with the atoms to which they are bonded, form an aromatic ring.
- 107. A method for preparing a compound having the following formula (CXIV):
- 108. for preparing a compound having the following formula (CXIV):
- 109. A method according to claim 108, wherein R1 and R3, together with the atoms to which they are bonded, form an aromatic ring.
Parent Case Info
[0001] This application claims the benefit of U.S. Provisional Patent Application Serial No. 60/315,147, filed Aug. 27, 2001, which is hereby incorporated by reference.
Government Interests
[0002] The present invention was made with the support of the National Science Foundation, Contract No. CHE 0092490, and the National Institutes of Health, Contract No. CA85641 and Contract No. GM57425. The Federal Government may have certain rights in this invention.
Provisional Applications (1)
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Number |
Date |
Country |
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60315147 |
Aug 2001 |
US |