Catalytic asymmetric epoxidation
| Foreign code | F110005243 |
|---|---|
| File No. | B12-01US1 |
| Posted date | Aug 29, 2011 |
| Country | United States of America |
| Application number | 65689107 |
| Gazette No. | 20070203347 |
| Gazette No. | 7714167 |
| Date of filing | Jan 22, 2007 |
| Gazette Date | Aug 30, 2007 |
| Gazette Date | May 11, 2010 |
| Priority data |
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| Title |
Catalytic asymmetric epoxidation
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| Abstract |
(US7714167) The present invention relates to the synthesis of chiral epoxides via a catalytic asymmetric oxidation of olefins. Additionally, the methodology provides a method of asymmetrically oxidizing sulfides and phosphines. This asymmetric oxidation employs a catalyst system composed of a metal and a chiral bishydroxamic acid ligand, which, in the presence of a stoichiometric oxidation reagent, serves to asymmetrically oxidize a variety of substrates. |
| Scope of claims |
[claim1] 1. A chiral bishydroxamic acid ligand of a structure I: wherein: R1, R2, R3, R4, R5 and R6 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, aryl, heteroaryl, and arylalkyl; or wherein R1 and R2, together with the atom to which they are attached, form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, heterocyclyl, and aryl; or wherein R4 and R5, together with the atom to which they are attached, form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, heterocyclyl, and aryl; R7, R8, R9, and R10 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, aryl, heteroaryl, and arylalkyl; or wherein R7 and R9, together with the atoms to which they are attached, form a substituted or non-substituted ring selected from the group consisting of cycloalkyl and heterocyclyl; -Z- is selected from the group consisting of -- CO(O) -- and -- S(O)2 -- . [claim2] 18. A method of performing a catalytic asymmetric oxidation comprising: reacting a substrate with catalytic amounts of a chiral bishydroxamic acid ligand and a metal, in the presence of an oxidation reagent, to produce a chiral oxidation product; wherein the substrate is selected from the group consisting of sulfide and phosphine; wherein the chiral bishydroxamic acid ligand is of formula (I): wherein: R1, R2, R3, R4, R5, and R6 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, aryl, heteroaryl, and arylalkyl; or wherein R1 and R2, together with the atom to which they are attached, form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, heterocyclyl, and aryl; or wherein R4 and R5, together with the atom to which they are attached, form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, heterocyclyl, and aryl; R7, R8, R9, and R10 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, aryl, heteroaryl, and arylalkyl; or wherein R7 and R9, together with the atoms to which they are attached, form a substituted or non-substituted ring selected from the group consisting of cycloalkyl and heterocyclyl; -Z- is selected from the group consisting of -- CO(O) -- and -- S(O)2 -- or the chiral bishydroxamic acid ligand is of formula (Ib') or (Ic'): wherein: R13, R14, R15, R16, R17, and R18 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, awl, heteroaryl, and arylalkyl; R19 and R20 are each independently selected from the group consisting of hydrogen, halogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, awl, heteroaryl, and arylalkyl; R21, R22, R23, and R24 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, aryl, heteroaryl, and arylalkyl; and R25 and R26 are each independently selected from the group consisting of hydrogen, halogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, aryl, heteroaryl, and arylalkyl. [claim3] 2. The ligand of claim 1, wherein R1, R2, R3, R4, R5, and R6 are each independently selected from the group consisting of hydrogen, alkyl, alkyloxy, and alkylamino. [claim4] 3. The ligand of claim 1, wherein R1, R2, R3, R4, R5, and R6 are each independently selected from the group consisting of cycloalkyl and heterocyclyl. [claim5] 4. The ligand of claim 1, wherein R1, R2, R3, R4, R5, and R6 are each independently selected from the group consisting of aryl, arylalkyl, heteroaryl, and halogen. [claim6] 5. The ligand of claim 1, wherein: R1 and R2, together with the atom to which they are attached, form a substituted or unsubstituted ring; R4 and R5, together with the atom to which they are attached, form a substituted or unsubstituted ring; and the ring formed by R1 and R2 is identical to the ring formed by R4 and R5. [claim7] 6. The ligand of claim 1, wherein R7, R8, R9, and R10 are each independently selected from the group consisting of hydrogen, alkyl, alkyloxy, and alkylamino. [claim8] 7. The ligand of claim 1, wherein R7, R8, R9, and R10 are each independently selected from the group consisting of cycloalkyl and heterocyclyl. [claim9] 8. The ligand of claim 1, wherein R7, R8, R9, and R10 are each independently selected from the group consisting of awl, arylalkyl, and heteroaryl. [claim10] 9. The ligand of claim 1, wherein R7 and R9, together with the atoms to which they are attached, form a ring. [claim11] 10. The ligand of claim 9, wherein R8 and R10 are identical. [claim12] 11. The ligand of claim 7, wherein R7 and R9, together with the atoms to which they are attached, form a ring. [claim13] 12. The ligand of claim 11, wherein R8 and R10 are identical. [claim14] 13. The ligand of claim 1, wherein: R1 and R2 are awl groups; R3 is hydrogen; R4 and R5 are awl groups; and R6 is hydrogen. [claim15] 14. The ligand of claim 13, wherein: R1 and R2 are identical; and R4 and R5 are identical. [claim16] 15. The ligand of claim 14, wherein R1, R2, R4, and R5 are identical. [claim17] 16. The ligand of claim 1, wherein the chiral bishydroxamic acid ligand (I) is selected from the group consisting of: [claim18] 17. A chiral bishydroxamic acid ligand, selected from the following formulae: wherein: R13, R14, R15, R16, R17, and R18 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, aryl, heteroaryl, and arylalkyl; R19 and R20 are each independently selected from the group consisting of hydrogen, halogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, aryl, heteroaryl, and arylalkyl; R21, R22, R23, and R24 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, aryl, heteroaryl, and arylalkyl; R25 and R26 are each independently selected from the group consisting of hydrogen, halogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, aryl, heteroaryl, and arylalkyl. [claim19] 19. The method of claim 18, wherein the metal is selected from the group consisting of molybdenum (IV), molybdenum (V), and molybdenum (VI). [claim20] 20. The method of claim 18, wherein the oxidation reagent is an organic hydroperoxide with the following structure (II): R11 -- O -- OH II wherein R11 is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and heterocyclyl. |
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| IPC(International Patent Classification) |
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| Reference ( R and D project ) | SORST Selected in Fiscal 2000 |
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