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EP-4735170-A1 - METATHESIS COMPOSITIONS COMPRISING AIR-STABLE IMIDO ALKYLIDENE COMPLEXES

EP4735170A1EP 4735170 A1EP4735170 A1EP 4735170A1EP-4735170-A1

Abstract

The invention relates to a composition comprising a Schrock-alkylidene complex bearing a neutral ligand selected from 1,10-phenanthroline and 2,2'-bipyridine, and a one or more compound(s) comprising an olefinic double bond, respectively. When the complexes are non-dissociative, they can be thermoactivated to initiate a metathesis reaction in the composition. The invention further relates to a composition comprising a Schrock-alkylidene complex bearing a neutral 2,2'-bipyridine ligand, and one or more compound(s) comprising an olefinic double bond, respectively, wherein the complex is autoactivating.

Inventors

  • GULYÁS, Henrik
  • TSCHAN, Mathieu Jean-Luc Joseph

Assignees

  • Verbio SE

Dates

Publication Date
20260506
Application Date
20240628

Claims (17)

  1. CLAIMS 1. Composition capable of performing a metathesis reaction, the composition comprising: (X) a 14-electron Schrock alkylidene compound complexed with a bidentate ligand selected from (a) a 1,10-phenanthroline (optionally substituted) and (b) a 2,2’-bipyridine (optionally substituted); to form a 18-electron alkylidene compound; and (Y) one or more compounds each comprising an olefinic double bond; wherein the composition (c) does not contain a Lewis acid selected from one or more of MgCl2, MgBr2, MgI 2 , MnCl 2 , MnBr 2 , MnI 2 , FeCl 3 , AlCl 3 , CuCl 2 , ZnCl 2 , ZnBr 2 , ZnI 2 , Zn(triflate) 2 or Zn(trifluoroacetate) 2 ; (d) is at a temperature above 50 °C; preferably wherein the composition (e) does not contain an inert solvent for the compound (X) and/or (Y). 2. Composition of claim 1, comprising: (X1) a compound of formula I I wherein M is Mo or W; A is selected from N-R 1 or O, wherein R 1 is C1-10 alkyl or aryl, optionally respectively substituted; B is selected from pyrrole, indole and pyrazole, optionally respectively substituted; and C is selected from O-R 2 , wherein R 2 is C1-10 alkyl or aryl, or (C1-10alkyl)3Si or (aryl)3Si, optionally respectively substituted; or B is identical to C, wherein C is selected from O-R 2 , wherein R 2 is C 1-10 alkyl or aryl, or (C1-10alkyl)3Si or (aryl)3Si, optionally respectively substituted; or B is different from C, wherein both B and C are selected from O-R 2 , wherein R 2 is C 1-10 alkyl or aryl, or (C 1-10 alkyl) 3 Si or (aryl) 3 Si, optionally respectively substituted; D is 1,10-phenanthroline or substituted 1,10-phenanthroline; R 3 and R 4 are independently H, C 1-10 alkyl or aryl, C 1-10 alkyl and aryl being optionally substituted; and wherein only one of R 3 and R 4 is hydrogen; or comprising (X2) a compound of formula II II wherein M is Mo or W; A is selected from N-R 1 or O, wherein R 1 is C 1-10 alkyl or aryl, optionally respectively substituted; B is selected from pyrrole, indole and pyrazole, optionally respectively substituted; and C is selected from O-R 2 , wherein R 2 is C1-10 alkyl or aryl, or (C1-10alkyl)3Si or (aryl)3Si, optionally respectively substituted; or B is identical to C, wherein C is selected from O-R 2 , wherein R 2 is C 1-10 alkyl or aryl, or (C1-10alkyl)3Si or (aryl)3Si, optionally respectively substituted; or B is different from C, wherein both B and C are selected from O-R 2 , wherein R 2 is C 1-10 alkyl or aryl, or (C 1-10 alkyl) 3 Si or (aryl) 3 Si, optionally respectively substituted; D is 2,2’-bipyridine or substituted 2,
  2. 2’-bipyridine; R 3 and R 4 are independently H, C 1-10 alkyl or aryl, C 1-10 alkyl and aryl being optionally substituted; and wherein only one of R 3 and R 4 is hydrogen.
  3. 3. Composition of claim 2, wherein R 1 is C1-10 alkyl or phenyl, respectively independently substituted with one or more of C 1-10 alkyl, C 1-10 alkoxy, phenyl, halogen, CN, and CF 3 .
  4. 4. Composition of any one of claims 2 to 3, wherein B is selected from pyrrole, indole and pyrazole, respectively independently substituted with one or more of C 1-10 alkyl, C1-10 alkoxy or phenyl.
  5. 5. Composition of any one of claims 2 to 4, wherein R 2 is selected from C1-10 alkyl or phenyl, optionally substituted.
  6. 6. Composition of any one of claims 1 to 5, wherein the compound (X) or the compound (X1) and (X2) is/are non-dissociative in the composition at least up to room temperature.
  7. 7. Composition of any one of claims 2 to 6, wherein C is an electron-withdrawing group, and 1,10-phenanthroline is unsubstituted; or C is an electron-withdrawing group, and 1,10-phenanthroline is substituted with one or more electron-donating groups; or B is identical to C, wherein C is an electron-withdrawing group, and 1,10- phenanthroline is unsubstituted; or B is identical to C, wherein C is an electron-withdrawing group, and 1,10- phenanthroline is substituted with one or more electron-donating groups; or B is different from C, wherein both B and C are electron-withdrawing groups, and 1,10-phenanthroline is unsubstituted; or B is different from C, wherein both B and C are electron-withdrawing groups, and 1,10-phenanthroline is substituted with one or more electron-donating groups; or B is identical to C, wherein C is an electron-withdrawing group, and 2,2’-bipyridine is unsubstituted; or B is identical to C, wherein C is an electron-withdrawing group, and 2,2’-bipyridine is substituted with one or more electron-donating groups; or B is different from C, wherein both B and C are electron-withdrawing groups, and 2,2’-bipyridine is unsubstituted; or B is different from C, wherein both B and C are electron-withdrawing groups, and 2,2’-bipyridine is substituted with one or more electron-donating groups; preferably wherein B is selected from pyrrole, indole and pyrazole, optionally respectively substituted, and C is selected from O-R 2 , wherein R 2 is C1-10 alkyl or aryl, or (C1- 1 0 alkyl) 3 Si or (aryl) 3 Si, respectively substituted with one or more of halogen or CF 3 ; and 1,10-phenanthroline is unsubstituted or is 1,10-phenanthroline substituted with one or more selected from C1-5 alkyl, C1-5 alkoxy, -O-(CH2)n-O- (n = 1 or 2), and phenyl; or B is identical to C, wherein C is selected from O-R 2 , wherein R 2 is C 1-10 alkyl or aryl, or (C1-10alkyl)3Si or (aryl)3Si, respectively substituted with one or more of halogen or CF3; and 1,10-phenanthroline is unsubstituted or 1,10-phenanthroline is substituted with one or more selected from C 1-5 alkyl, C 1-5 alkoxy, -O-(CH 2 ) n -O- (n = 1 or 2), and phenyl; or B is identical to C, wherein C is selected from O-R 2 , wherein R 2 is C1-10 alkyl or aryl, or (C 1-10 alkyl) 3 Si or (aryl) 3 Si, respectively substituted with one or more of halogen or CF3; and 2,2’-bipyridine is unsubstituted or is substituted with one or more selected from C1-5 alkyl, C1-5 alkoxy, or phenyl.
  8. 8. Composition of any one of claims 6 or 7, wherein the compound is non- dissociative up to a temperature of 50 °C.
  9. 9. Composition of any one of claims 2 to 8, wherein R 3 and R 4 are independently H, C1-10 alkyl or aryl, wherein C1-10 alkyl or aryl are independently substituted with one or more of C 1-5 alkyl, C 1-5 alkyl substituted with one or more of halogen, C 1-5 alkoxy, phenyl, halogen; or wherein the molar ratio of compound(s) (Y) comprising one or more compounds each comprising an olefinic double bond to the compound (X) or (X1) of formula I or to the compound (X2) of formula II in a composition which has a temperature of 50 °C or below is greater than 2000 or 4000 or 6000 or 8000 or 10,000 or 20,000 or 30,000 or 40,000 compared to the composition which has the temperature above 50 °C; or wherein the temperature is above 55 °C or above 60 °C or above 70 °C or above 80 °C or above 90 °C or above 100 °C; or wherein the temperature is in a range of from above 50 to 140 °C or above 55 to 130 °C or above 60 to 120 °C.
  10. 10. Composition of any of claims 1 to 9, wherein the compound (X) is selected from one of the following compounds 5 to 8: wherein R 24 = methyl, phenyl; R 25 , R 26 = H, methyl, CF3; Z =methyl, iso-propyl, halogen; or is selected from one of the following compounds III to VI or is selected from one of the following compounds: R = Me, Ph; Ar = 2,6-diisopropylphenyl; ; or is selected from .
  11. 11. The composition of any one of claims 1 to 10, wherein the compound (X) has a stability constant which exceeds a value of 250,000 L*mol -1 at 298 K in a solvent, wherein the solvent is the one or more compounds (Y) each comprising an olefinic double bond, and/or wherein the solvent is an inert solvent for the compound (X) and/or (Y), the stability constant being determined as defined in the description.
  12. 12. The composition of any one of claims 1 to 11, wherein the stability constant is more than 300,000 L*mol -1 or more than 350,000 L*mol -1 or more than 400,000 L*mol -1 .
  13. 13. Method of making a composition as defined in any one of claims 1 to 12, comprising: providing a compound (X) and a compound (Y); heating a mixture of the provided compounds to a temperature above 50 °C; wherein the composition does not contain a Lewis acid selected from one or more of MgCl 2 , MgBr 2 , MgI 2 , MnCl 2 , MnBr 2 , MnI 2 , FeCl 3 , AlCl 3 , CuCl 2 , ZnCl 2 , ZnBr 2 , ZnI 2 , Zn(triflate) 2 or Zn(trifluoroacetate) 2 ; preferably wherein the composition does not contain an inert solvent for the compound (X) and/or (Y).
  14. 14. Method of activating a compound (X) as defined in any one of claims 1 to 12 for initiating an olefinic metathesis reaction in a composition comprising one or more compound(s) (Y) each comprising an olefinic double bond, the method comprising: heating a composition comprising the compounds (X) and (Y) to a temperature above 50 °C; wherein the composition does not contain a Lewis acid selected from one or more of MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, Zn(triflate) 2 or Zn(trifluoroacetate) 2 ; preferably wherein the composition does not contain an inert solvent for the compound (X) and/or (Y); or method of performing a metathesis reaction, the method comprising: heating a composition comprising a compound (X) and one or more compounds (Y) as defined in any one of claims 1 to 10 to a temperature above 50 °C, wherein the composition does not contain a Lewis acid selected from one or more of MgCl 2 , MgBr 2 , MgI 2 , MnCl 2 , MnBr 2 , MnI 2 , FeCl 3 , AlCl 3 , CuCl 2 , ZnCl 2 , ZnBr 2 , ZnI 2 , Zn(triflate)2 or Zn(trifluoroacetate)2; preferably wherein the composition does not contain an inert solvent for the compound (X) and/or (Y).
  15. 15. Composition, comprising: a compound (X) and one or more compounds (Y) as defined in any one of claims 1 to 12; wherein the composition does not contain a Lewis acid selected from one or more of MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI 2 , Zn(triflate) 2 or Zn(trifluoroacetate) 2 ; wherein the composition has a temperature below 50 °C; preferably wherein the composition does not contain an inert solvent for the compound (X) and/or (Y).
  16. 16. Use of the composition as defined in claim 15 in a metathesis reaction, the use comprising: heating the composition above a temperature of 50 °C.
  17. 17. Use of a compound (X) for initiating a metathesis reaction in a composition comprising one or more compound(s) (Y) as defined in any one of claims 1 to 12, the use comprising: heating a composition comprising the compounds (X) and (Y) to a temperature above 50 °C; wherein the composition does not contain a Lewis acid selected from one or more of MgCl 2 , MgBr 2 , MgI 2 , MnCl 2 , MnBr 2 , MnI 2 , FeCl 3 , AlCl 3 , CuCl 2 , ZnCl 2 , ZnBr 2 , ZnI 2 , Zn(triflate)2 or Zn(trifluoroacetate)2; preferably wherein the composition does not contain an inert solvent for the compound (X) and/or (Y).

Description

Verbio Vereinigte BioEnergie AG 119468P771PC MR/ABB METATHESIS COMPOSITIONS COMPRISING AIR-STABLE IMIDO ALKYLIDENE COMPLEXES FIELD OF THE INVENTION [0001] The invention relates to a composition capable of performing a metathesis reaction, the composition comprising a 18-electron molybdenum or tungsten alkylidene complex formed by a 14-electron molybdenum or tungsten alkylidene complex and a 1,10-phenanthroline or a 2,2’-bipyridine as a neutral bidentate ligand and one or more compounds comprising each an olefinic double bond. The complexes comprised in the compositions may be activated by heat to initiate a metathesis reaction. The invention further relates to a method of making the composition, and to a method of activating the composition. BACKGROUND OF THE INVENTION [0002] Olefin metathesis reactions catalyzed by transition metal catalysts such as molybdenum or tungsten alkylidene catalysts - so-called Schrock catalysts - are among the most important reactions of organic synthetic chemistry. A valuable type of known catalysts is the group of Mo(VI) and W(VI) alkylidene complexes. The efficacy thereof depends on the type of metal, alkylidene group and ligands. While such catalysts have proved effective, they frequently lack stability in air which makes them more difficult to handle and often restricts their usefulness. [0003] For improving air-stability, WO 2012/116695 (Fürstner) suggests stabilizing such catalysts by complexing them with bidentate heterocycles such as 1,10- phenanthroline and 2,2’-bipryridine. Exemplified 1,10-phenanthroline complexes are e.g. complexes 5 to 8 wherein R24 = methyl, phenyl; R25, R26 = H, methyl, CF3; Z =methyl, iso-propyl, halogen. [0004] However, such an air-stable product is not active catalytically, but the active form of the catalyst was known to be released by exposure to a Lewis acid such as MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, Zn(triflate)2 or Zn(trifluoroacetate)2. Presence of Lewis acids and the formation of adducts of phenanthroline with the Lewis acid generally results in a complex work-up of the reaction mixture to isolate the products of the reaction. [0005] EP 3268377 B1 (XiMo AG) discloses tungsten imido alkylidene catalysts stabilized with 1,10-phenanthroline. The catalysts must be activated by addition of a Lewis acid such as zinc chloride. The activation is performed in an inert solvent such as toluene. Exemplified complexes are complexes III to VI: [0006] The scientific publication from J. Heppekausen and A. Fürstner, “Rendering Schrock-type Molybdenum Alkylidene Complexes Air Stable: User-friendly Precatalysts for Alkene Metathesis”, Angew. Chem. Int. Ed. 2011, 50, 7829-7832, https://doi.org/10.1002/anie.201102012, discloses phenanthroline and bipyridine complexes 2, 3, 5, and 7 of Schrock catalysts which give no indications for partial dissociation (to 1, 4, or 6) in a solvent at room temperature as determined by NMR spectroscopy: Ar=2,6-diisopropylphenyl. [0007] The authors state that complexes 2, 3, 5, and 7 are devoid of catalytic activity even at higher temperatures. [0008] GB 2537416 discloses in Examples 3 and 6 metathesis catalysts complexed with 2,2’-bipyridine and a substituted bipyridine which may be activated by dissolution in an aprotic solvent such as deuterobenzene without the need for the addition of a Lewis acid because they spontaneously dissociate (see Examples 10 and 11 of GB 2537416). The inventors of GB 2537416 term the spontaneous liberation of the active catalyst in a solvent as an “autoactivating catalyst”. [0009] This reference further discloses the homo-metathesis reaction of allylbenzene at room temperature catalyzed by . without using a solvent. The complex is autoactivating at room temperature, i.e., the complex dissociates into the 14-electron system and bipyridine. The conversion after 16 h was 54.2 %. [0010] The concept of autoactivating bipyridine adducts has also been published in the scientific literature (Gulyás, H. et al. “Air-stable 18-electron adducts of Schrock catalysts with tuned stability constants for spontaneous release of the active species”, Commun. Chem. 4, 71 (2021); https:/doi.org/10.1038/s42004-021-00503-4). This reference discloses the homo-metathesis of methyl oleate in benzene at a temperature of 80 °C, and the ring-closing metathesis of diethyl diallyl malonate in benzene at room temperature using as catalyst the compound . [0011] This reference further discloses the ring-opening metathesis polymerization of norbornene in toluene at 25 °C using as catalyst the compound . [0012] WO 2021/239891 (Verbio) discloses Schrock-alkylidene complexes comprising a phenanthrene ligand D of the following formula as defined therein: . [0013] The inventors of WO 2021/239891 discovered that Schrock-alkylidene complexes of the above formula having a stability constant in the range of from 5 L*mol- 1 to 250,000 L*mol-1 when measured at 298 K and