Chiral catalysts and catalytic epoxidation catalyzed thereby

• US 5,637,739 A
• Filed: 10/15/1992
• Issued: 06/10/1997
• Est. Priority Date: 03/21/1990
• Status: Expired due to Term

• Current Assignee: Research Corporation Technologies
• Original Assignee: Research Corporation Technologies
• Inventors: Deng, Li, Jacobsen, Eric N., Zhang, Wei
• Primary Examiner(s): NAZARIO GONZALEZ, PORFIRIO
• Application Number:
  US07/938,245
• Time in Patent Office: 1,699 Days
• Field of Search: 556/42, 556/45, 556/56, 556/57, 556/137, 556/150, 556/510, 556/524, 556/525, 556/531, 556/533, 556/537, 556/167, 502/167, 549/510, 549/524, 549/525, 549/531, 549/533, 549/537
• US Class Current: 549/524
• CPC Class Codes: B01J 2231/72 Epoxidation
• CPC Class Codes: B01J 2531/0252 Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
• CPC Class Codes: B01J 2531/0266 Axially chiral or atropisomeric ligands, e.g. bulky biaryls such as donor-substituted binaphthalenes, e.g. "BINAP" or "BINOL"
• CPC Class Codes: B01J 2531/72 Manganese
• CPC Class Codes: B01J 31/2243 At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
• CPC Class Codes: C07C 251/24 having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
• CPC Class Codes: C07C 2601/14 The ring being saturated
• CPC Class Codes: C07C 315/02 by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
• CPC Class Codes: C07D 301/12 with hydrogen peroxide or inorganic peroxides or peracids
• CPC Class Codes: C07D 301/14 with organic peracids, or salts, anhydrides or esters thereof
• CPC Class Codes: C07D 303/04 containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
• CPC Class Codes: C07D 303/48 with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
• CPC Class Codes: C07D 305/14 condensed with carbocyclic rings or ring systems
• CPC Class Codes: C07D 493/04 Ortho-condensed systems
• CPC Class Codes: C07D 493/10 Spiro-condensed systems
• CPC Class Codes: C07F 13/005 Compounds without a metal-carbon linkage
• CPC Class Codes: C07F 19/005 without metal-C linkages
• CPC Class Codes: C07F 7/0803 Compounds with Si-C or Si-Si linkages
• CPC Class Codes: C07F 7/081 comprising at least one atom selected from the elements N, O, halogen, S, Se or Te

Abstract

Methods of using chiral catalysts for enantioselectively epoxidizing a prochiral olefin and for enantioselectively oxidizing a prochiral sulfide are disclosed. In accordance with one aspect of the invention, the catalyst used is a salen derivative which has the following general structure: ##STR1## In accordance with another aspect of the present invention is a method of producing an epoxychroman using a chiral catalyst. In accordance with this method, a chromene derivative, an oxygen atom source, and a chiral catalyst are reacted under such conditions and for such time as is needed to epoxidize said chromene derivative. In accordance with yet another aspect of this invention is a method of enantioselectively epoxidizing a cis-cinnamate derivative to make taxol or an analog thereof. In accordance with another aspect a method of disproportionation of hydrogen peroxide using the catalysts of the present invention is disclosed.

Claims

1. A chiral catalyst having the following general formula:

##STR91## where M is a transition metal ion in the +3 oxidation state;

where A is an anion;

where n is either 3, 4, 5 or 6;

where at least one of X1 or X2 is selected from the group consisting of aryls, primary alkyls, secondary alkyls, tertiary alkyls, and alkyl groups bearing hetero atoms;

where at least one of X3 or X4 is selected from the group consisting of aryls, primary alkyls, secondary alkyls, tertiary alkyls, and alkyl groups bearing hetero atoms;

where at least one of Y1 or Y2 is selected from the group consisting of aryls, primary alkyls, secondary alkyls, tertiary alkyls, halides, NO₂ and alkyl groups bearing hetero atoms;

where at least one of Y4 or Y5 is selected from the group consisting of aryls, primary alkyls, secondary alkyls, tertiary alkyls, halides, NO₂ and alkyl groups bearing hetero atoms;

where Y3, and Y6 are independently selected from the group consisting of hydrogen and primary alkyl groups;

where R1 and R4 are trans to each other and at least one of R1 and R4 is selected from the group consisting of primary alkyls and hydrogen; and

where the carbons in the (C)_n portion have substituents selected from the group consisting of hydrogen, alkyl, aryl, and hetero atoms.

2. The catalyst of claim 1 wherein the metal ion is Mn.

3. The catalyst of claim 1 wherein R1 is the same as R4.

4. The catalyst of claim 1 wherein X1 and X3 are independently selected from the group consisting of t-butyl and phenyl.

5. The catalyst of claim 1 wherein Y1 and Y4 are independently selected from the group consisting of t-butyl and phenyl.

6. The catalyst of claim 1 wherein Y1 and Y4 are independently selected from the group consisting of t-butyl, phenyl, halides, O--CH₃ and NO₂.

7. The catalyst of claim 1 wherein X1, X3, Y1 and Y4 are all the same.

8. The catalyst of claim 1 wherein X1, X3, Y1 and Y4 are all t-butyl.

9. The catalyst of claim 8 wherein R1 and R4 are hydrogen.

10. The catalyst of claim 1 wherein n is 4.

11. The catalyst of claim 10 wherein Y1 and Y4 are selected from the group consisting of t-butyl, phenyl, halides, O--CH₃ and NO₂.

12. The catalyst of claim 11 wherein R1 and R4 are hydrogen.

13. The catalyst of claim 12 wherein the transition metal is Mn and the anion is Cl.

33. A method of enantioselectively epoxidizing a prochiral olefin with the use of a chiral catalyst comprising the steps of:

providing a prochiral olefin;

providing an oxygen atom source;

providing the chiral catalyst of claim 1, 14, 18 or 30; and

reacting said olefin, said oxygen atom source, and said chiral catalyst under such conditions and for such time sufficient to epoxidize said olefin.

34. The method of claim 33 wherein the prochiral olefin is selected from the group consisting of monosubstituted and cis 1,2 disubstituted olefins.

35. The method of claim 33 wherein the prochiral olefin is a cis disubstituted olefin bearing a primary substituent on one side of the double bond and a secondary, tertiary, or aryl substituent on the other side.

36. The method of claim 33 wherein the olefin is selected from the group consisting of:

cis-β

-methylstyrene, dihydronaphthalene, 2-cyclohexenyl-1,1-dioxolane,

2,2-dimethylchromene, styrene, and propylene.

37. The method of claim 33 wherein the oxygen atom source is selected from the group consisting of NaOCl, iodosylmesitylene, NalO₄, NBu₄ IO₄, potassium peroxymonosulfate, magnesium monoperoxyphthalate, and hexacyanoferrate ion.

38. The method of claim 33 wherein the oxygen atom source is selected from group consisting of NaOCl and iodosylmesitylene.

39. The method of claim 33 further comprising the step of adding a pyridine-N-oxide derivative to the olefin, the oxygen atom source, and the chiral catalyst.

40. The method of claim 39 wherein the pyridine-N-oxide derivative is selected from the group consisting of 4-phenylpyridine-N-oxide and 4-t-butylpyridine-N-oxide.

41. The method of claim 39 wherein the olefin is selected from the group consisting of cis-β

-methylstyrene, dihydronaphthalene, 2-cyclohexenyl-1,1-dioxolane, 2,2-dimethylchromene, styrene, and propylene.

42. A method of enantioselectively epoxidizing a chromene derivative with a chiral catalyst comprising the steps of:

providing a chromene derivative having the general formula;

##STR95## wherein R1, R2, R3, R4, X1, X2, X3 and X4 are each selected from the group consisting of hydrogen, aryls, primary alkyls, secondary alkyls, tertiary alkyls, alkyl groups bearing hetero atoms, and silyls, and wherein no more than one of R1 and R2 are hydrogen;

providing an oxygen atom source;

providing the chiral catalyst of claim 1, 14, 18 or 30; and

reacting said chromene derivative, said oxygen atom source, and said chiral catalyst under such conditions and for such time sufficient to epoxidize said chromene derivative, to thereby produce an epoxychroman.

43. The method of claim 42 wherein R1 and R2 on the chromene derivative are the same.

44. The method of claim 42 wherein the R1 and R2 on the chromene derivative are alkyl groups.

45. The method of claim 42 wherein R1 and R2 on the chromene derivative are methyl groups.

46. The method of claim 42 wherein the chromene derivative is 6-cyano-2,2-dimethylchromene.

47. The method of claim 42 wherein the oxygen atom source is NaOCl.

48. The method of claim 42 wherein the transition metal ion is selected from the group consisting of Mn, Cr, Fe, Ni, and Co.

49. The method of claim 42 further comprising the step of adding a pyridine-N-oxide derivative to the chromene derivative, the oxygen atom source, and the chiral catalyst.

50. The method of claim 49 wherein the pyridine-N-oxide derivative is selected from the group consisting of 4-phenylpyridine-N-oxide and 4-t-butylpyridine-N-oxide.

51. The method of claim 42 wherein the opposite enantiomer of the chiral catalyst is included to thereby produce a racemic mixture of the epoxychroman.

52. A method of enantioselectively epoxidizing a cis-cinnamate derivative with a chiral catalyst to produce a cis-epoxide of said cinnamate derivative, said method comprising the steps of:

providing a cis-cinnamate derivative having the general formula;

##STR96## wherein A1-A5 are each selected from the group consisting of hydrogen, aryls, primary alkyls, secondary alkyls, tertiary alkyls, hydroxyl, alkoxy groups, F, Cl, Br, I, and amines;

providing an oxygen atom source;

providing the chiral catalyst defined in claim 1, 14, 18 or 30; and

reacting said cis-cinnamate derivative, said oxygen atom source, and said chiral catalyst under such conditions and for such time sufficient to epoxidize said cis-cinnamate derivative, to thereby produce a cis-epoxide of said cinnamate derivative.

53. The method of claim 52 further comprising the step of adding a pyridine-N-oxide derivative to the cis-cinnamate, the oxygen atom source, and the chiral catalyst.

54. The method of claim 53 wherein said pyridine-N-oxide derivative is selected from the group consisting of 4-phenylpyridine-N-oxide and 4-t-butylpyridine-N-oxide.

55. The method of claim 52 wherein the A1-A5 groups on the cis-cinnamate derivative are all the same.

56. The method of claim 52 wherein the A1-A5 groups on the cis-cinnamate derivative are hydrogen.

57. The method of claim 52 wherein R1 on the cis-cinnamate derivative is an ethyl group.

58. The method of claim 52 wherein the cis-cinnamate derivative is cis-ethyl cinnamate.

59. The method of claim 52 wherein the oxygen atom source is NaOCl.

60. The method of claim 52 wherein the transition metal ion is manganese.

14. A chiral catalyst having the following general formula:

##STR92## where M is a transition metal in the +3 oxidation state;

where A is an anion; and

where R1 and R4 are trans to each other and at least one of R1 and R4 is selected from the group consisting of primary alkyls and hydrogen.

15. The catalyst of claim 14 wherein the metal ion is Mn.

16. The catalyst of claim 15 wherein the anion is Cl.

17. The catalyst of claim 14 wherein R1 and R4 are hydrogen.

18. A chiral catalyst having the following general formula when in the active state:

##STR93## where M is a transition metal ion in the +3 oxidation state;

where n is either 3, 4, 5 or 6;

where at least one of X1 or X2 is selected from the group consisting of aryls, primary alkyls, secondary alkyls, tertiary alkyls, and alkyl groups bearing hetero atoms;

where at least one of X3 or X4 is selected from the group consisting of aryls, primary alkyls, secondary alkyls, tertiary alkyls, and alkyl groups bearing hetero atoms;

where at least one of Y1 or Y2 is selected from the group consisting of aryls, primary alkyls, secondary alkyls, tertiary alkyls, halides, NO₂ and alkyl groups bearing hetero atoms;

where at least one of Y4 or Y5 is selected from the group consisting of aryls, primary alkyls, secondary alkyls, tertiary alkyls, halides, NO₂ and alkyl groups bearing hetero atoms;

where Y3, and Y6 are independently selected from the group consisting of hydrogen and primary alkyl groups;

where R1 and R4 are trans to each other and at least one of R1 and R4 is selected from the group consisting of primary alkyls and hydrogen; and

where the carbons in the (C)_n portion have substituents selected from the group consisting of hydrogen, alkyl, aryl, and hetero atoms.

19. The catalyst of claim 18 wherein the metal ion is Mn.

20. The catalyst of claim 18 wherein R1 is the same as R4.

21. The catalyst of claim 18 wherein X1 and X3 are independently selected from the group consisting of t-butyl and phenyl.

22. The catalyst of claim 18 wherein Y1 and Y4 are independently selected from the group consisting of t-butyl and phenyl.

23. The catalyst of claim 18 wherein Y1 and Y4 are independently selected from the group consisting of t-butyl, phenyl, halides, O--CH₃ and NO₂.

24. The catalyst of claim 18 wherein X1, X3, Y1 and Y4 are all the same.

25. The catalyst of claim 18 wherein X1, X3, Y1 and Y4 are all t-butyl.

26. The catalyst of claim 25 wherein R1 and R4 are hydrogen.

27. The catalyst of claim 18 wherein n is 4.

28. The catalyst of claim 27 wherein Y1 and Y4 are selected from the group consisting of t-butyl, phenyl, halides, O--CH₃ and NO₂.

29. The catalyst of claim 28 wherein R1 and R4 are hydrogen.

30. A chiral catalyst having the following general formula:

##STR94## where M is a transition metal;

where R1 and R4 are trans to each other and at least one of R1 and R4 is selected from the group consisting of primary alkyls and hydrogen.

31. The catalyst of claim 30 wherein the metal ion is Mn.

32. The catalyst of claim 30 wherein R1 and R4 are hydrogen.