Catalytic carbonylation of three and four membered heterocycles

• US 6,852,865 B2
• Filed: 12/02/2002
• Issued: 02/08/2005
• Est. Priority Date: 12/06/2001
• Status: Expired due to Term

• Current Assignee: Cornell Research Foundation Incorporated (Cornell University)
• Original Assignee: Cornell Research Foundation Incorporated (Cornell University)
• Inventors: Mahadevan, Viswanath, Getzler, Yutan D. Y. L., Coates, Geoffrey W., Wolczanski, Peter
• Primary Examiner(s): Tsang, Cecilia J.
• Assistant Examiner(s): COVINGTON, RAYMOND K
• Application Number:
  US10/307,520
• Publication Number:
  US 20030162961A1
• Time in Patent Office: 799 Days
• Field of Search: 549/88, 549/96, 549/510, 549/512, 556/27, 556/45, 556/57, 556/76, 556/182, 548/950, 548/952, 548/953, 548/959, 548/965, 502/161
• US Class Current: 548/950
• CPC Class Codes: B01J 2231/34 Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
• CPC Class Codes: B01J 2531/0208 Bimetallic complexes, i.e. comprising one or more units of two metals, with metal-metal bonds but no all-metal (M)n rings, e.g. Cr2(OAc)4
• CPC Class Codes: B01J 2531/025 Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
• CPC Class Codes: B01J 2531/0252 Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
• CPC Class Codes: B01J 2531/31 Aluminium
• CPC Class Codes: B01J 2531/38 Lanthanides other than lanthanum
• CPC Class Codes: B01J 2531/46 Titanium
• CPC Class Codes: B01J 2531/62 Chromium
• CPC Class Codes: B01J 2531/845 Cobalt
• CPC Class Codes: B01J 31/183 with more than one complexing nitrogen atom, e.g. phenanthroline
• CPC Class Codes: B01J 31/20 Carbonyls
• CPC Class Codes: B01J 31/2208 Oxygen, e.g. acetylacetonates
• 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: B01J 31/2295 Cyclic compounds, e.g. cyclopentadienyls
• CPC Class Codes: C07D 205/08 with one oxygen atom directly attached in position 2, e.g. beta-lactams
• CPC Class Codes: C07D 205/12 condensed with carbocyclic rings or ring systems
• CPC Class Codes: C07D 265/06 not condensed with other rings
• CPC Class Codes: C07D 305/12 Beta-lactones
• CPC Class Codes: C07D 305/14 condensed with carbocyclic rings or ring systems
• CPC Class Codes: C07D 307/33 in position 2, the oxygen atom being in its keto or unsubstituted enol form
• CPC Class Codes: C07D 315/00 : Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00
• CPC Class Codes: C07F 15/065 : without a metal-carbon linkage

Abstract

Epoxides, aziridines, thiiranes, oxetanes, lactones, lactams and analogous compounds are reacted with carbon monoxide in the presence of a catalytically effective amount of catalyst having the general formula [Lewis acid]^z+{[QM(CO)_x]^w−}_y where Q is any ligand and need not be present, M is a transition metal selected from the group consisting of Groups 4, 5, 6, 7, 8, 9 and 10 of the periodic table of elements, z is the valence of the Lewis acid and ranges from 1 to 6, w is the charge of the metal carbonyl and ranges from 1 to 4 and y is a number such that w times y equals z, and x is a number such as to provide a stable anionic metal carbonyl for {[QM(CO)_x]^w−}_y and ranges from 1 to 9 and typically from 1 to 4.

Claims

1. A process for the carbonylation of a compound having the formula:

where R₁, R₂, R₃ and R₄ are selected from the group consisting of hydrogen, C₁-C_100,000-alkyl, C₂-C_100,000-alkenyl and C₆-C_100,000-aryl, where the alkyl, alkenyl and aryl are optionally substituted with halogen or benzyl ether, and alkylaryl, ester, ketone, alcohol, acid, aldehyde, amide and tosyl containing from 1 to 20 carbon atom, and benzyl ether, alkyl substituted silyl ether where the ether group is C₁-C₆ alkylene and alkyl substitution consists of one to three C₁-C₆ alkyl(s) substituted on silyl, and any other functionality that the catalyst referred to below is tolerant of, and where R₂ and R₄ can join to form a ring, and X is selected from the group consisting of O, S and NR₅ where R₅ is selected from the group consisting of hydrogen, C₁-C_100,000-alkyl, C₂-C_100,000-alkenyl and C₆-C_100,000-aryl where the alkyl alkenyl and aryl are optionally substituted with halogen or benzyl ether, and alkylaryl, ester, ketone, alcohol, acid, aldehyde, amide and tosyl containing from 1 to 20 carbon atoms, and benzyl ether, alkyl substituted silyl ether where the ether group is C₁-C₆-alkylene and where the alkyl substitution consists of one to three C₁-C₆ alkyl(s) substituted on silyl, and any other functionality that the catalyst referred to below is tolerant of and does not cause rearrangement, and where n is 0 or 1, and Y is C═

O or CH₂, said process comprising the step of reacting compound (I) with carbon monoxide in the presence of a catalytically effective amount of catalyst having the general formula [Lewis acid]^z+{[QM(CO)_x]^w−

}_y where Q is any ligand and need not be present, M is a transition metal selected from the group consisting of Groups 4, 5, 6, 7, 8, 9 and 10 of the periodic table of elements, z is the valence of the Lewis acid and ranges from 1 to 6, w is the charge of the metal carbonyl and ranges from 1 to 4 and y is a number such that w times y equals z, and x is a number such as to provide a stable anionic metal carbonyl for {[QM(CO)_x]^w−

}_y, to form a product having the structural formula;

where R₁, R₂, R₃ and R₄ and X correspond to R₁, R₂, R₃, R₄ and X in (I) including R₂ and R₄ forming a ring if that is the case for (I); and

in the case where n for (I) is 0, n for (II) is 0 or 1, and in the case where n for (I) is 1, n for (II) is 1;

said catalyst excluding catalyst formed from the combination of a cobalt source and a hydroxy substituted pyridine.

2. The process of claim 1 where n for (I) is 0 so that the structural formula for (I) becomes:

and the product has the structural formula;

n is 1 and Y is C═

O.

3. The process of claim 2 where the catalyst is [(salph)Al(THF)₂][Co(CO)₄] where THF is tetrahydrofuran and which has the structural formula:

where So is tetrahydrofuran and ^tBu is t-butyl.

4. The process of claim 3 wherein the reaction is carried out at a carbon monoxide pressure ranging from 100 to 10,000 psi and a temperature ranging from 0°

to 120°

C. in the presence of catalyst in a mole ratio of compound (III) to catalyst (cobalt basis) ranging from 1;

1 to 10,000;

1.

5. The process of claim 4 where X for (III) is O.

6. The process of claim 4 where the compound (III) is propylene oxide.

7. The process of claim 4 where the compound (III) is (R)-propylene oxide and the product is (R)-β

-butyrolactone.

8. The process of claim 7 where the reaction is carried out at a pressure ranging from 850 to 900 psi and a temperature ranging from 0 to 120°

C., over a time period ranging from 0.75 to 1.5 hours.

9. The process of claim 4 where the compound (III) is 1-butene oxide.

10. The process of claim 4 where the compound (III) is epichlorohydrin.

11. The process of claim 4 where the compound (III) is isobutylene oxide.

12. The process of claim 4 where the compound (III) is 2,3-epoxybutane.

13. The process of claim 4 where X is NR₅.

14. The process of claim 13 where the compound (III) is 1-benzyl-2-methyl aziridine.

15. The process of claim 13 where the compound (III) is 1-tosyl-2-methylaziridine.

16. The process of claim 13 where the compound (III) is cis-1-benzyl-2-(tert-butyldimethylsiloxymethyl)-3-methyl aziridine.

17. The process of claim 2 where the catalyst is

where ^tBu is t-butyl and So is tetrahydrofuran.

18. The process of claim 17 where the reaction is carried out at a carbon monoxide pressure ranging from 100 to 10,000 psi and a temperature ranging from 0°

C. to 120°

C. in the presence of catalyst in a mole ratio of compound (III) to catalyst (cobalt basis ranging from 1;

1 to 10,000;

1.

19. The process of claim 18 where X for (III) is O.

20. The process of claim 19 where the compound (III) is benzyl glycidyl ether.

21. The process of claim 2 where the catalyst is

where So is tetrahydrofuran and Ph is phenyl.

22. The process of claim 21 where the reaction is carried out at a carbon monoxide pressure ranging from 100 to 10,000 psi and a temperature ranging from 0°

C. to 120°

C. in the presence of catalyst in a mole ratio of compound (III) to catalyst (cobalt basis) ranging from 1;

1 to 10,000;

1.

23. The process of claim 22 where X for (III) is O.

24. The process of claim 23 where the compound (III) is 1-butene oxide.

25. The process of claim 23 where the compound (III) is 1-heptene oxide.

26. The process of claim 23 where the compound (III) is cyclooctene oxide.

27. The process of claim 2 where the catalyst has the structure

where M is a metal such that (VI) is stable.

28. The process of claim 27 where the catalyst has the structure (VI) where M is titanium with a valence of three.

29. The process of claim 28 where the reaction is carried out at a carbon monoxide pressure ranging from 100 to 10,000 psi and a temperature ranging from 0°

C. to 120°

C. in the presence of a catalyst in a mole ratio of compound (III) to catalyst (cobalt basis) ranging from 1;

1 to 10,000;

1.

30. The process of claim 29 where X for the compound (III) is O.

31. The process of claim 30 where the compound (III) is propylene oxide.

32. The process of claim 31 where the compound (III) is R-propylene oxide.

33. The process of claim 30 where the compound (III) is 1,2-epoxybutane.

34. The process of claim 30 where the compound (III) is 1,2-epoxy-5-hexene.

35. The process of claim 30 where the compound (III) is epichlorohydrin.

36. The process of claim 30 where the compound (III) is isobutylene oxide.

37. The process of claim 30 where the compound (III) is cis-2,3-epoxybutane.

38. The process of claim 30 where the compound (III) is trans-2,3-epoxybutane.

39. The process of claim 29 where X for the compound (III) is NR₅.

40. The process of claim 39 where the compound (III) is 1-benzyl-2-methyl aziridine.

41. The process of claim 39 where the compound (III) is 7-benzyl-7-azabicyclo[4.1.0]heptane.

42. The process of claim 39 where the compound (III) is 1-tosyl-2-methylaziridine.

43. The process of claim 39 where the compound (III) is cis-1-benzyl-2-(tert-butylmethylsilyloxymethyl)-3-methylaziridine.

44. The process of claim 1 where n for (I) is 1 and Y is C═

O or CH₂.

45. The process of claim 44 where the catalyst has the structure

where THF is tetrahydrofuran and ^tBu is t-butyl and M is Al.

46. The process of claim 45 where the reaction is carried out at a carbon monoxide pressure ranging from 100 to 10,000 psi and a temperature ranging from 0°

C. to 120°

C. in the presence of a catalyst in a mole ratio of compound (I) to catalyst (cobalt basis) ranging from 1;

1 to 10,000;

1.

47. The process of claim 46 where the compound (I) is oxetane.

48. The process of claim 46 where Y is C═

O and R₁ and R₃ for the compound (I) are both H.

49. The process of claim 48 where R₄ for the compound (I) is H.

50. The process of claim 49 where R₂ for the compound (I) is Me.

51. The process of claim 44 where the catalyst has the structure

where M is titanium with a valence of three.

52. The process of claim 51 where the reaction is carried out at a carbon monoxide pressure ranging from 100 to 10,000 psi and a temperature ranging from 0°

C. to 120°

C. in the presence of a catalyst in a mole ratio of compound (I) to catalyst (cobalt basis) ranging from 1;

1 to 10,000;

1.

53. The process of claim 52 where Y is C═

O.

54. The process of claim 53 where R₁, R₃ and R₄ for the compound (I) are H.

55. The process of claim 54 where R₂ for the compound (I) is Me.

56. The process of claim 54 where R₂ for the compound (I) is Et.

57. The process of claim 54 where R₂ for the compound (I) is CCl₃.

58. The process of claim 52 where R₁, R₂ and R₄ for the compound (I) are H.

59. The process of claim 58 where R₃ for the compound (I) is Me.

60. The process of claim 58 where R₃ for the compound (I) is Ph.

61. The process of claim 44 where the catalyst has the structure

where M is samarium with a valence of three.

62. The process of claim 61 where the reaction is carried out at a carbon monoxide pressure ranging from 100 to 10,000 psi and a temperature ranging from 0°

C. to 120°

C. in the presence of a catalyst in a mole ratio of compound (I) to catalyst (cobalt basis) ranging from 1;

1 to 10,000;

1.

63. The process of claim 62 where Y is C═

CO and R₁, R₃ and R₄ for the compound (I) are H and R₂ for the compound (I) is Me.

64. The process of claim 1 where in the [Lewis acid]^z+ portion of the catalyst a neutral two electron donor is present and fills the coordination valence of the cationic Lewis acid.

65. The process of claim 64 where the [Lewis acid]^z+ portion of the catalyst contains an aluminum or chromium center.

66. The process claim 65 where the neutral two electron donor is tetrahydrofuran.

67. The process of claim 1 where the catalyst has the structure

where M is a metal such that (VI) is stable.

68. The process of claim 67 where the reaction is carried out at a carbon monoxide pressure ranging from 100 to 10,000 psi and a temperature ranging from 0°

C. to 120°

C. in the presence of a catalyst in a mole ratio of compound (I) to catalyst (cobalt basis) ranging from 1;

1 to 10,000;

1.

85. The process of claim 1 where the [Lewis acid]^z+ portion of the catalyst does not contain a neutral two electron donor.

86. The process of claim 7 where the yield of (R)-β

-butyrolactone is greater than 95%.

87. The process of claim 1 wherein in the formula (I), at least one of R₁, R₂, R₃ and R₄ is not hydrogen.

69. A process for the carbonylation of a compound having the formula

where Ph is phenyl, said process comprising the step of reacting compound (XI) with carbon monoxide in the presence of a catalytically effective amount of catalyst having the general formula [Lewis acid]^z+{[QM(CO)_x]^w−

}_y where Q is any ligand and need not be present, M is a transition metal selected from the group consisting of Groups 4, 5, 6, 7, 8, 9 and 10 of the periodic table of elements, z is the valence of the Lewis acid and ranges from 1 to 6, w is the charge of the metal carbonyl and ranges from 1 to 4 and y is a number such that w times y equals z, and x is a number such as to provide a stable anionic metal carbonyl for {[QM(CO)_x]^w−

}_y, to form a product which comprises a mixture of

70. A compound having the structural formula:

where ^tBu is t-butyl and So is a neutral two electron donor.

71. The compound of claim 70 where the neutral two electron donor is tetrahydrofuran.

72. A compound having the structural formula:

where the ^tBu is t-butyl and So is a neutral two electron donor.

73. The compound of claim 72 where the neutral two electron donor is tetrahydrofuran.

74. A compound having the structural formula:

where ^tBu is t-butyl and So is a neutral two electron donor.

75. The compound of claim 74 where the neutral two electron donor is tetrahydrofuran.

76. A compound having the structure:

where THF is tetrahydrofuran and ^tBu is t-butyl.

77. The compound of claim 76 where M is Al.

78. The compound of claim 76 where M is Cr.

79. A compound having the structure:

where ^tBu is t-butyl and So is a neutral two electron donor.

80. The compound of claim 79 where the neutral two electron donor is tetrahydrofuran.

81. A compound having the structure:

where Ph is phenol and So is a neutral two electron donor.

82. The compound of claim 81 where the neutral two electron donor is tetrahyrofuran.

83. 9-Oxa-bicyclo[6.2.0]decan-10-one.

84. 13-Oxa-bicyclo[10.2.0]tetradecan-14-one.