Catalytic asymmetric epoxidation
外国特許コード | F110003521 |
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整理番号 | B12-01US |
掲載日 | 2011年6月28日 |
出願国 | アメリカ合衆国 |
出願番号 | 76202804 |
公報番号 | 20050159607 |
公報番号 | 7202371 |
出願日 | 平成16年1月20日(2004.1.20) |
公報発行日 | 平成17年7月21日(2005.7.21) |
公報発行日 | 平成19年4月10日(2007.4.10) |
発明の名称 (英語) |
Catalytic asymmetric epoxidation
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発明の概要(英語) |
(US7202371) 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. |
特許請求の範囲(英語) |
[claim1] 1. A method of performing a catalytic asymmetric epoxidation comprising: reacting an alkene or cyclic alkene with catalytic amounts of a chiral bishydroxamic acid ligand and a metal, in the presence of an oxidation reagent, to produce a chiral epoxide, where the chiral bishydroxamic acid ligand has a structure I: where: 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 where 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 where 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 where 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 -- C(O) -- and -- S(O)2 -- . [claim2] 2. The method of claim 1, where the metal is selected from the group consisting of vanadium (IV), vanadium (V), molybdenum (IV), molybdenum (V), and molybdenum (VI). [claim3] 3. The method of claim 2, where the metal is selected from the group consisting of vanadium (IV) and vanadium (V). [claim4] 4. The method of claim 2, where the metal is selected from the group consisting of molybdenum (IV), molybendum (V), and molybendum (VI). [claim5] 5. The method of claim 1, where the oxidation reagent is an organic hydroperoxide with the following structure (II): R11 -- O -- OH II where, R11 is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and heterocyclyl. [claim6] 6. The method of claim 1, where R1, R2, R3, R4, R5, and R6 are each independently selected from the group consisting of hydrogen, alkyl, alkyoxy, and alkylamino. [claim7] 7. The method of claim 1, where R1, R2, R3, R4, R5, and R6 are each independently selected from the group consisting of cycloalkyl and heterocyclyl. [claim8] 8. The method of claim 1, where R1, R2, R3, R4, R5, and R6 are each independently selected from the group consisting of aryl, arylalkyl, heteroaryl, and halogen. [claim9] 9. The method of claim 1, where: 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. [claim10] 10. The method of claim 1, where R7, R8, R9, and R10 are each independently selected from the group consisting of hydrogen, alkyl, alkyoxy, and alkylamino. [claim11] 11. The method of claim 1, where R7, R8, R9, and R10 are each independently selected from the group consisting of cycloalkyl and heterocyclyl. [claim12] 12. The method of claim 1, where R7, R8, R9, and R10 are each independently selected from the group consisting of aryl, arylalkyl, and heteroaryl. [claim13] 13. The method of claim 1, where R7 and R9, together with the atoms to which they are attached, form a ring. [claim14] 14. The method of claim 13, where R8 and R10 are identical. [claim15] 15. The method of claim 11, where R7 and R9, together with the atoms to which they are attached, form a ring. [claim16] 16. The method of claim 15, where R8 and R10 are identical. [claim17] 17. The method of claim 1, where: R1 and R2 are aryl groups;R3 is hydrogen;R4 and R5 are aryl groups; and R6 is hydrogen. [claim18] 18. The method of claim 17, where: R1 and R2 are identical; and R4 and R5 are identical. [claim19] 19. The method of claim 18, where R1, R2, R4, and R5 are identical. [claim20] 20. The method of claim 1, where the chiral bishydroxamic acid ligand (I) is selected from the group consisting of: [claim21] 21. The method of claim 2, where the metal is selected from the group consisting of VO(OPr)i, VO(acac)2, VO(OEt)3, and MoO2(acac)2. [claim22] 22. The method of claim 5, where the organic hydroperoxide is selected from the group consisting of tert-butyl hydroperoxide and cumene hydroperoxide. [claim23] 23. The method of claim 5, where the organic hydroperoxide is tert-butyl hydroperoxide. [claim24] 24. The method of claim 5, where the organic hydroperoxide is cumene hydroperoxide. [claim25] 25. The method of claim 2, where the oxidation reagent is selected from the group consisting of tert-butyl hydroperoxide and cumene hydroperoxide. [claim26] 26. The method of claim 2, where the oxidation reagent is tert-butyl hydroperoxide. [claim27] 27. The method of claim 2, where the oxidation reagent is cumene hydroperoxide. [claim28] 28. The method of claim 1, where the oxidation reagent is hydrogen peroxide. [claim29] 29. The method of claim 2, where the oxidation reagent is hydrogen peroxide. [claim30] 30. A method of performing a catalytic asymmetric epoxidation comprising: reacting an alkene or cyclic alkene with catalytic amounts of a chiral bishydroxamic acid ligand and a metal, in the presence of an oxidation reagent, to produce a chiral epoxide, where the chiral bishydroxamic acid ligand is selected from the following formulae: where: 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. [claim31] 31. The method of claim 1, where the alkene is of the formula (X): where: R23, R24, R25, and R26 are each independently selected from the group consisting of hydrogen, halogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, aryl, heteroaryl, and arylalkyl. [claim32] 32. The method of claim 1, where the alkene is a cyclic alkene of the formula (Xa): where: R27 and R28 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, aryl, aralklyl, heteroaryl, halogen, and alkene;n is 1, 2, 3, 4, 5, or 6;each X is independently selected from the group consisting of CR'R'', -- NR' -- , and -- O -- ; R' and R'' are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, aryl, aralklyl, heteroaryl, and halogen. [claim33] 33. The method of claim 31, where the chiral oxidation product is of the formula (Xb): [claim34] 34. The method of claim 32, where the chiral oxidation product is of the formula (Xc): [claim35] 35. The method of claim 1, where the reacting step is carried out in a solvent. [claim36] 36. The method of claim 35, where the reacting step is carried out in a solvent selected from the group consisting of methylene chloride, toluene, chloroform, and ethyl acetate. [claim37] 37. The method of claim 1, where the reacting step is carried out at a temperature of about -20 to about 25 deg. C. [claim38] 38. The method of claim 1, where the reaction is carried out with about 0.001 to about 0.1 equivalents of the chiral bishydroxamic acid ligand (I). [claim39] 39. The method of claim 1, where the reaction is carried out with about 0.005 to about 0.05 equivalents of metal. |
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国際特許分類(IPC) |
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参考情報 (研究プロジェクト等) | SORST Selected in Fiscal 2000 |
日本語項目の表示
発明の名称 |
C-2対称軸を有するビスヒドロキシサム酸の合成-不斉酸化反応における有効なリガンド(A CATALYTIC ASYMMETRIC EPOXIDATION)
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