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Catalytic asymmetric epoxidation achieved

Foreign code F110003521
File No. B12-01US
Posted date Jun 28, 2011
Country United States of America
Application number 76202804
Gazette No. 20050159607
Gazette No. 7202371
Date of filing Jan 20, 2004
Gazette Date Jul 21, 2005
Gazette Date Apr 10, 2007
Title Catalytic asymmetric epoxidation achieved
Abstract (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.
Scope of claims [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.
  • Inventor, and Inventor/Applicant
  • YAMAMOTO HISASHI
  • BASAK ARINDRAJIT
  • ZHANG WEI
  • JAPAN SCIENCE AND TECHNOLOGY AGENCY
  • UNIVERSITY OF CHICAGO
IPC(International Patent Classification)
Reference ( R and D project ) SORST Selected in Fiscal 2000
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