CATALYTIC CARBONYLATION CATALYSTS AND METHODS

Abstract

In one aspect, the present invention provides catalysts for the carbonylation of heterocycles. The inventive catalysts feature metal-ligand complexes having cationic functional groups tethered to the ligand, wherein the tethered cationic groups are associated with anionic metal carbonyl species. The invention also provides methods of using the inventive catalysts to affect the ring opening carbonylation of epoxides.

Claims

1-26. (canceled)

27. A catalyst comprising: i) a metal complex of formula (III-a), (III-b), (III-c), (IV-a), (IV-b), (IV-c), (V-a), (V-b), (VI-a), (VI-b), or (VI-c): ##STR00342## ##STR00343## ##STR00344## wherein: R.sup.c, R.sup.d and R.sup.e at each occurrence is independently: ##STR00345## wherein: is a bond or a linker; Z.sup.+ is a cationic functional group; and b is an integer from 1 to 4 inclusive; or hydrogen, halogen, OR.sup.4, NR.sup.y.sub.2, SR.sup.y, CN, NO.sub.2, SO.sub.2R.sup.y, SOR.sup.y, SO.sub.2NR.sup.y.sub.2; CNO, NR.sup.ySO.sub.2R.sup.y, NCO, N.sub.3; or an optionally substituted group selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, wherein two or more R.sup.c groups, or two or more R.sup.d groups may be taken together to form one or more optionally substituted rings, wherein each R.sup.y is independently hydrogen, or an optionally substituted group selected the group consisting of acyl; carbamoyl; arylalkyl; 6- to 10-membered aryl; C.sub.1-12 aliphatic; C.sub.1-12 heteroaliphatic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; an oxygen protecting group; and a nitrogen protecting group; or wherein two R.sup.y on the same nitrogen atom are taken with the nitrogen atom to form an optionally substituted 4- to 7-membered heterocyclic ring having 0-2 additional heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; R.sup.4 is a hydroxyl protecting group or R.sup.y; R.sup.12 is selected from the group consisting of: a ##STR00346## group; or an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; and phenyl; and M.sup.1 and M.sup.2 comprise metal atoms, and may be the same or different; and ii) at least one anionic metal carbonyl species associated with at least one of Z.sup.+.

28. (canceled)

29. The catalyst of claim 27, wherein M.sup.1 and M.sup.2 are independently selected from the group consisting of Zn(II), Cu(II), Mn(II), Co(II), Ru(II), Fe(II), Rh(II), Ni(II), Pd(II), Mg(II), Al(III), Cr(III), Cr(IV), Ti(IV), Fe(III), Co(III), Ti(III), In(III), Ga(III), and Mn(III).

30. The catalyst of claim 27, wherein M.sup.1 and M.sup.2 are aluminum.

31. The catalyst of claim 27, wherein M.sup.1 and M.sup.2 are chromium.

32. The catalyst of claim 27, wherein Z.sup.+ comprises an atom selected from the group consisting of nitrogen, phosphorous, arsenic, and sulfur.

33. The catalyst of claim 27, wherein at least one anionic metal carbonyl species is X.sup. and is associated with at least one of Z.sup.+, wherein Z.sup.+X.sup. is selected from the group consisting of: ##STR00347## ##STR00348## or a combination of two or more of these, wherein: each R.sup.1 and R.sup.2 is independently hydrogen or an optionally substituted group selected from the group consisting of: C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7- to 14-membered saturated or partially unsaturated polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; an 8- to 14-membered polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; phenyl; and an 8- to 14-membered polycyclic aryl ring; or wherein R.sup.1 and R.sup.2 are taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more additional heteroatoms; each R.sup.3 is independently hydrogen or an optionally substituted group selected from the group consisting of: C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7- to 14-membered saturated or partially unsaturated polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; an 8- to 14-membered polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; phenyl; and an 8- to 14-membered polycyclic aryl ring; or wherein an R.sup.3 group are taken with an R.sup.1 or R.sup.2 group to form one or more optionally substituted rings; and R.sup.5 is R.sup.2 or hydroxyl; or wherein R.sup.1 and R.sup.5 are taken together with intervening atoms to form one or more optionally substituted carbocyclic, heterocyclic, aryl, or heteroaryl rings; each R.sup.6 and R.sup.7 is independently hydrogen or an optionally substituted group selected from the group consisting of: C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7- to 14-membered saturated or partially unsaturated polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; an 8- to 14-membered polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; phenyl; and an 8- to 14-membered polycyclic aryl ring; or wherein R.sup.6 and R.sup.7 are taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms, or an R.sup.6 and R.sup.7 group are taken with an R.sup.1 or R.sup.2 group to form one or more optionally substituted rings; each occurrence of R.sup.8 is independently: halogen, NO.sub.2, CN, SR.sup.y, S(O)R.sup.y, S(O).sub.2R.sup.y, NR.sup.yC(O)R.sup.y, OC(O)R.sup.y, CO.sub.2R.sup.y, NCO, N.sub.3, OR.sup.7, OC(O)N(R.sup.y).sub.2, N(R.sup.y).sub.2, NR.sup.yC(O)R.sup.y, or NR.sup.yC(O)OR.sup.y; or an optionally substituted group selected from the group consisting of: C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7- to 14-membered saturated or partially unsaturated polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; an 8- to 14-membered polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; phenyl; and an 8- to 14-membered polycyclic aryl ring; wherein each R.sup.y is independently H, or an optionally substituted group selected from the group consisting of C.sub.1-6 aliphatic, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, a 3-7 membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, a 5-6 membered heteroaryl ring having 1-3 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, and an 8- to 10-membered aryl; or wherein two or more adjacent R.sup.8 groups are taken together to form an optionally substituted saturated, partially unsaturated, or aromatic 5- to 12-membered ring containing 0 to 4 heteroatoms; Ring A is an optionally substituted, 5- to 10-membered heteroaryl group; and Ring B is an optionally substituted, 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 0-2 heteroatoms in addition to the depicted ring nitrogen atom independently selected from the group consisting of nitrogen, oxygen, and sulfur; wherein: when is a bond, is the site of attachment of Z.sup.+ to the metal complex; when is a linker, is the site of attachment of Z.sup.+ to the linker.

34. The catalyst of claim 27, wherein the linker comprises 1-30 atoms including at least one carbon atom and optionally one or more atoms selected from the group consisting of N, O, S, Si, B, and P.

35. The catalyst of claim 27, wherein the linker is an optionally substituted C.sub.2-30 aliphatic group wherein one or more methylene units are optionally and independently replaced by: -Cy-, NR.sup.y, N(R.sup.y)C(O), C(O)N(R.sup.y), O, C(O), OC(O), C(O)O, S, SO, SO.sub.2, C(S), C(NR.sup.y), or NN, wherein each -Cy- is independently an optionally substituted 5-8 membered bivalent, saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; or an optionally substituted 8-10 membered bivalent saturated, partially unsaturated, or aryl bicyclic ring having 0-5 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; and each R.sup.y is independently H, or an optionally substituted group selected from the group consisting of: C.sub.1-6 aliphatic, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, a 3-7 membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, a 5-6 membered heteroaryl ring having 1-3 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, and an 8- to 10-membered aryl.

36. The catalyst of claim 27, wherein the at least one anionic metal carbonyl species is a compound of formula: [Q.sub.dM.sub.e(CO).sub.w].sup.y, wherein: Q is a ligand and need not be present, M is a metal atom, d is an integer between 0 and 8 inclusive, e is an integer between 1 and 6 inclusive, w is a number such as to provide a stable anionic metal carbonyl complex, and y is the charge of the anionic metal carbonyl species.

37. The catalyst of claim 36, wherein Q is a phosphine ligand or a cyclopentadienyl (cp) ligand.

38. The catalyst of claim 27, wherein the at least one anionic metal carbonyl species is selected from the group consisting of: monoanionic carbonyl complexes of metals from groups 5, 7 or 9 of the periodic table, and dianionic carbonyl complexes of metals from groups 4 or 8 of the periodic table.

39. The catalyst of claim 27, wherein the at least one anionic metal carbonyl species is selected from the group consisting of: [Co(CO).sub.4].sup., [Ti(CO).sub.6].sup.2, [V(CO).sub.6].sup., [Rh(CO).sub.4].sup., [Fe(CO).sub.4].sup.2, [Ru(CO).sub.4].sup.2, [Os(CO).sub.4].sup.2, [Cr.sub.2(CO).sub.10].sup.2, [Fe.sub.2(CO).sub.8].sup.2, [Tc(CO).sub.5].sup., [Re(CO).sub.5].sup., and [Mn(CO).sub.5].sup..

40. The catalyst of claim 27, wherein the at least one anionic metal carbonyl species is [Co(CO).sub.4].sup..

41. A catalyst selected from the group consisting of: ##STR00349## ##STR00350## ##STR00351## ##STR00352## ##STR00353## ##STR00354## ##STR00355## ##STR00356## ##STR00357## ##STR00358## ##STR00359## ##STR00360## ##STR00361## ##STR00362## ##STR00363## ##STR00364## ##STR00365## ##STR00366## ##STR00367## ##STR00368## ##STR00369## ##STR00370## ##STR00371## ##STR00372## ##STR00373## ##STR00374## ##STR00375## ##STR00376## ##STR00377## ##STR00378## ##STR00379## ##STR00380## ##STR00381## ##STR00382## ##STR00383## ##STR00384## wherein each M independently comprises a metal atom.

42. The catalyst of claim 41, wherein each M is independently selected from the group consisting of Zn(II), Cu(II), Mn(II), Co(II), Ru(II), Fe(II), Rh(II), Ni(II), Pd(II), Mg(II), Al(III), Cr(III), Cr(IV), Ti(IV), Fe(III), Co(III), Ti(III), In(III), Ga(III), and Mn(III).

43. The catalyst of claim 41, wherein each M is independently aluminum or chromium.

44. A method comprising contacting ethylene oxide with carbon monoxide in the presence of a catalyst of claim 27, to provide a product comprising beta propiolactone, succinic anhydride, or polypropiolactone, or a mixture of any two or more of these.

45. The method of claim 44, wherein the product comprises beta propiolactone, polypropiolactone, or a combination thereof.

46. A method comprising contacting propylene oxide with carbon monoxide in the presence of a catalyst of claim 27, to provide a product comprising beta butyrolactone, methyl succinic anhydride, or poly-3-hydroxybutyrate, or a mixture of any two or more of these.

47. The method of claim 46, wherein the product comprises beta butyrolactone, poly-3-hydroxybutyrate, or combination thereof.

48. A method comprising contacting ethylene oxide with carbon monoxide in the presence of a catalyst of claim 41, to provide a product comprising beta propiolactone, succinic anhydride, or polypropiolactone, or a mixture of any two or more of these.

49. The method of claim 48, wherein the product comprises beta propiolactone, polypropiolactone, or a combination thereof.

50. A method comprising contacting propylene oxide with carbon monoxide in the presence of a catalyst of claim 41, to provide a product comprising beta butyrolactone, methyl succinic anhydride, or poly-3-hydroxybutyrate, or a mixture of any two or more of these.

51. The method of claim 50, wherein the product comprises beta butyrolactone, poly-3-hydroxybutyrate, or a combination thereof.

52. A catalyst comprising: i) a metal complex of formulae: ##STR00385## wherein: R.sup.d and R.sup.e at each occurrence is independently: ##STR00386## wherein: is a bond or a linker; Z.sup.+ is a cationic functional group; and b is an integer from 1 to 4 inclusive; or hydrogen, halogen, OR.sup.4, NR.sup.y.sub.2, SR, CN, NO.sub.2, SO.sub.2R.sup.y, SOR.sup.y, SO.sub.2NR.sup.y.sub.2; CNO, NR.sup.ySO.sub.2R.sup.y, NCO, N.sub.3; or an optionally substituted group selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, wherein two or more R.sup.d groups may be taken together to form one or more optionally substituted rings, wherein each R.sup.y is independently hydrogen, or an optionally substituted group selected the group consisting of acyl; carbamoyl; arylalkyl; 6- to 10-membered aryl; C.sub.1-12 aliphatic; C.sub.1-12 heteroaliphatic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; an oxygen protecting group; and a nitrogen protecting group; or wherein two R.sup.y on the same nitrogen atom are taken with the nitrogen atom to form an optionally substituted 4- to 7-membered heterocyclic ring having 0-2 additional heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; R.sup.4 is a hydroxyl protecting group or R.sup.y; and M.sup.1 and M.sup.2 comprise metal atoms, and may be the same or different; and ii) at least one anionic metal carbonyl species associated with at least one of Z.sup.+.

53. A catalyst selected from the group consisting of: ##STR00387## ##STR00388## ##STR00389## wherein each M independently comprises a metal atom.

Description

EXAMPLES

Example 1

[0302] A typical route to a salen aluminum (III) catalyst is shown in Scheme E1, below:

##STR00340##

[0303] As shown in Scheme E1, disubstituted phenol E1-a is formylated to provide salicylaldehyde derivative E1-b. Two equivalents of this aldehyde are then reacted with a diamine (in this case 1,2-benzenediamine) to afford Schiff base E1-c. This compound is then reacted with diethyl aluminum chloride and sodium cobalt tetracarbonyl to give the active Al(III)-salen catalyst. Similar chemistries can be applied to synthesis of the catalysts described hereinabove. One skilled in the art of organic synthesis can adapt this chemistry as needed to provide the specific catalysts described herein, though in some cases routine experimentation to determine acceptable reaction conditions and functional group protection strategies may be required.

Example 2

[0304] Synthesis of [{tetrakis-(N-methyl-4-pyridinium)-porphyrin}Al(THF).sub.2][Co(CO).sub.4].sub.5 is shown in Scheme E2, below:

##STR00341##

[0305] As shown in Scheme E2, pyrrole, pyridine-4-carbaldehyde and salicylic acid are refluxed in xylene to give porphyrin E2-a. E2-a is further reacted with MeCl to afford E2-b. E2-b is reacted with diethyl aluminum chloride and then with five equivalents of NaCo(CO).sub.4 in THF to afford the active Al(III)-salen catalyst E2-d. One skilled in the art of organic synthesis can adapt this chemistry as needed to provide the specific catalysts described herein, though in some cases routine experimentation to determine acceptable reaction conditions and functional group protection strategies may be required.

[0306] This application refers to various issued patents, published patent applications journal articles, and other publications all of which are incorporated herein by reference.

Other Embodiments

[0307] The foregoing has been a description of certain non-limiting embodiments of the invention. Accordingly, it is to be understood that the embodiments of the invention herein described are merely illustrative of the application of the principles of the invention. Reference herein to details of the illustrated embodiments is not intended to limit the scope of the claims, which themselves recite those features regarded as essential to the invention.