EP-4735457-A2 - E-SELECTIVE METATHESIS CATALYSTS

Abstract

The present invention relates to cationic molybdenum and tungsten complexes containing a heterocyclic nitrogen carbene (NHC) and preferably a halogen-containing aryloxy ligand. The catalysts are active in olefin metathesis reactions and provide for E-selectivity.

Inventors

• MEHDI, Hasan

Assignees

• Verbio SE

Dates

Publication Date

20260506

Application Date

20240628

Claims (1)

1. CLAIMS 1 . Compound of formula I [M(NHC)(X)(Y)(Z)(L) n ]A I wherein M is Mo or W; NHC is a nitrogen-containing heterocyclic carbene which binds via its carbene carbon atom to M; X is =NR 1 ; Y is an alkylidene or arylidene =CR 2 R 3 ; Z is an aryloxy residue -OR 4 ; L is a neutral ligand; n is 0 or 1 ; A is a non-coordinating anion; wherein R 1 is -C1-10 alkyl or -Ce-uaryl, optionally substituted, respectively; R 2 and R 3 are independently -Ci-walkyl or -Ce-uaryl, optionally substituted, respectively, or -H, wherein not both of R 2 and R 3 are H; R 4 is phenyl or phenyl substituted with at least one halogen atom; with the proviso that the compound of formula I is not a compound of one of the following formulae: , or Compound of formula II [M(NHC)(X)(Y)(Z)(L) n ]A II wherein M is Mo or W; preferably Mo; NHC is a nitrogen-containing heterocyclic carbene which binds via its carbene carbon atom to M; X is =NR 1 ; Y is an alkylidene or arylidene =CR 2 R 3 ; Z is an alkyloxy or aryloxy residue -OR 4 ; L is a neutral ligand; n is 0 or 1 ; A is a non-coordinating anion; wherein R 1 is -C1-10 alkyl or -Ce-uaryl, optionally substituted, respectively; R 2 and R 3 are independently -Ci-walkyl or -Ce-uaryl, optionally substituted, respectively, or -H, wherein not both of R 2 and R 3 are H; R 4 is -C1-10 alkyl or -Ce-uaryl, optionally substituted, respectively; with the proviso that the compound of formula II is not a compound of one of the following formulae: preferably wherein also the compounds of formula I as defined in claim 1 are excluded. 3. Compound of any one of claim 1 or 2, wherein NHC is selected from the group of following NHCs: a nitrogen-containing heterocyclic carbene containing the moiety of formula 6 wherein R 7 and R 8 as defined in formula 6 are each independently H, unbranched or branched C1-20 alkyl, C5-9 cycloalkyl, or phenyl, wherein the phenyl is optionally substituted with up to three groups independently selected from unbranched or branched C1-6 alkyl, C1-6 alkoxy or halogen, and wherein the chemical bonds which are symbolized with a wiggly line are connected to an optionally substituted alkenylene or alkylene group, respectively, wherein the carbene carbon atom, the two nitrogen atoms and the optionally substituted alkenylene or alkylene group form a ring; or a nitrogen-containing heterocyclic carbene containing the moiety of formula 7 7 wherein Ar as defined in formula 7 is aryl, preferably phenyl, optionally substituted with one or more groups selected from: C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, Ce-Cu aryl, C6-C14 aryloxy, or halogen; and wherein the chemical bonds which are symbolized with a wiggly line are connected to an optionally substituted alkenylene or alkylene group, respectively, wherein the carbon atom, the carbene carbon atom, the nitrogen atom and the optionally substituted alkenylene or alkylene group form a ring, which may optionally be bridged by an alkylene group; preferably wherein the carbene of formula 6 is a carbene of one of formulas 6a, 6b, 6c or 6d: 6b 6c or 6d wherein R 9 and R 10 are each independently H, unbranched or branched C1-20 alkyl, or phenyl, wherein phenyl is optionally substituted with up to three groups independently selected from unbranched or branched C1-6 alkyl, C1-6 alkoxy or halogen; or R 9 and R 10 together with the carbon atoms to which they are attached are combined to form a carbocyclic 3 to 8 membered ring, preferably an aryl ring, more preferably C6H4; Y and Y' are halogen; further preferably, wherein NHC is of formula 6a or 6b, preferably wherein R 9 and R 10 as defined in formula 6a or 6b are H, respectively, and R 7 and R 8 as defined in formula 6a and 6b are mesityl, or 2,6-diisopropylphenyl; or wherein NHC is of formula (n = 1-8). 4. Compound of any one of claims 1 to 3, wherein NHC is selected from: Compound of claim 3, wherein the carbene of formula 7 is a carbene of one of formulas 7a or 7b: wherein each R in formula 7a is independently hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, Ce-Cu aryl, C1-C5 perfluoroalkyl, C7-C24 aralkyl, or Ce-Cu perfluoroaryl group, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, Ce-Cu aryloxy, or a halogen atom; and wherein two R which are separated by the C-CR2-C moiety can be combined with to form a cyclic system; or a carbene of formula 7b 7b wherein each R in formula 7b is independently hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, Ce-Cu aryl, C1-C5 perfluoroalkyl, C7-C24 aralkyl, or Ce-Cu perfluoroaryl group, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, Ce-Cu aryloxy, or a halogen atom; and wherein n is 1 , 2 or 3; preferably wherein R in formula 7b are each independently hydrogen, C1-C12 alkyl, or C3-C12 cycloalkyl; preferably wherein the ligand of formula 7a is of formula 7a’ wherein R 12 , R 13 , R 14 , and R 15 in formula 7a’ are each independently hydrogen, C1- C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C6-C14 aryl, C1-C5 perfluoroalkyl, C7-C24 aralkyl, or C6-C14 perfluoroaryl group, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C6-C14 aryloxy, or a halogen atom; and wherein R 12 and/or R 13 can be combined with R 14 and/or R 15 to form a cyclic system; or wherein the ligand of formula 7b is of formula 7b’: wherein R 16 , R 17 and R 18 in formula 7b’ are each independently hydrogen or C1-C12 alkyl, or C3-C12 cycloalkyl, or C2-C12 alkenyl, C6-C14 aryl, C1-C5 perfluoroalkyl, C7-C24 aralkyl, or Ce-Cu perfluoroaryl group, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, Ce-Cu aryloxy, or a halogen atom, preferably wherein R 16 , R 17 and R 18 in formula 7b’ are each independently hydrogen, C1-C12 alkyl, or C3-C12 cycloalkyl; further preferably wherein NHC in formula 7 is a carbene of formula 7c wherein in formula 7c m is an integer of from 0 to 4, and each Ry independently has the meaning of C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C6-C14 aryl, C6-C14 aryloxy, or halogen; such as a carbene of formula 7c’ 7c’ or is a carbene of formula 7d wherein in formula 7d m is an integer of from 0 to 4, and each Ry independently has the meaning of C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C6-C14 aryl, C6-C14 aryloxy, or halogen; such as a carbene of formula 7d’ 7d’ or is a carbene of formula 7e or is a carbene of formula 7f or is a carbene of formula 7g or 7h or is a carbene of formula 7k and wherein each R in one of formulas 7c to 7i is independently hydrogen or C1-C12 alkyl, or C3-C12 cycloalkyl, or C2-C12 alkenyl, C6-C14 aryl, C1-C5 perfluoroalkyl, C7-C24 aralkyl, or C6-C14 perfluoroaryl group, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C6-C14 aryloxy, or a halogen atom; preferably wherein each R in formulas 7c to 7i is hydrogen, C1-C12 alkyl, or C3-C12 cycloalkyl. 6. Compound of any one of claims 1 and 3 to 5 as far as depending on claim 1 , wherein the term “optionally substituted” with regard to any of R 1 , R 2 , and R 3 , means that substituents are independently selected from the group consisting of Ci-salkyl, Cisalkoxy, halogen, nitro, N(Ci-salkyl)2, -NH-C(O)Ci-salkyl, phenyl, phenoxy, wherein phenyl and phenyl in phenoxy may be in turn substituted with one or more of Cisalkyl, Ci-salkoxy, halogen, nitro, N(Ci-salkyl)2, -NH-C(O)Ci-salkyl; or compound of any one of claims 2 and 3 to 5 as far as depending on claim 2, wherein the term “optionally substituted” with regard to any of R 1 , R 2 , R 3 , and R 4 means that substituents are independently selected from the group consisting of Ci-salkyl, Cisalkoxy, halogen, nitro, N(Ci-salkyl)2, -NH-C(O)Ci-salkyl, phenyl, phenoxy, wherein phenyl and phenyl in phenoxy may be in turn substituted with one or more of Ci- salkyl, Ci-salkoxy, halogen, nitro, N(Ci-salkyl)2, -NH-C(O)Ci-salkyl. 7. Compound of any one of claims 1 to 6, wherein one of R 2 and R 3 is hydrogen and the other one is -C(CH3)3 or -C(CH3)2C6Hs. 8. Compound of any one of claims 1 and 3 to 7 as far as depending on claim 1 , wherein R 4 is selected from phenyl; or from phenyl containing as at least one halogen only F; or from phenyl containing as at least one halogen only Cl; or from phenyl containing as at least one halogen only Br; or from phenyl containing as at least one halogen F and Cl; or from phenyl containing as at least one halogen F and Br; or from phenyl containing as at least one halogen Cl and Br; or from phenyl containing as at least one halogen F, Cl and Br. 9. Compound of any one of claims 1 to 8, wherein the neutral ligand L is selected from an ether, a phosphine, a nitrile, or a pyridine, dimethyl sulfoxide, acetone, dimethylformamide; preferably wherein the nitrile is selected from acetonitrile, t- butylnitrile, and benzonitrile. 10. Compound of any one of claims 1 to 9, wherein the non-coordinating anion is selected from the group consisting of perchlorate [CICU]’, tetrafluoro borate [BF4]", hexafluoro phosphate [PFe]’, hexafluoro antimonate [SbFe]-, tetraphenyl borate [BPh4]“, tetrakis(trifluoromethyl)borate [B(CF3)4]“, tetrakis(pentafluorophenyl)borate [B(C6FS)4] _ , tetrakis(3,5-bis-(trifluoromethyl)phenyl)borate [B{(3,5-di-CF3)C6H3}4]“, and tetrakis(nonafluoro-t-butoxy)aluminate [AI{OC(CF3)3}4]“. 11 . Compound of claim 1 , wherein the compound is characterized by formula [M(NHC)(=NAr)(=CHCMe 2 C6H5)(Z)(L)n]A and wherein the compound is selected from compounds X945 to X968 and X979 to X954 except compound X973 of the following table: Catalyst M Ar NHC Z L A- X945 Mo 2,6-Me 2 Ph IMes PhO - BArF X946 Mo 2,6-Me 2 Ph IMes 2-CIPhO - BArF X948 Mo 2,6-Me 2 Ph IMes 2,6-CI 2 PhO - BArF X949 Mo 2,6-Me 2 Ph IMes 2,5-CI 2 PhO - BArF X950 Mo 2,6-Me 2 Ph IMes 3,5-CI 2 PhO - BArF X956 Mo 2,6-Me 2 Ph SIMes 2,6-CI 2 PhO - BArF X957 Mo 2,6-CI 2 Ph IMes 2,6-CI 2 PhO - BArF X970 Mo 3,5-Me 2 Ph IMes 2,6-CI 2 PhO ACN BArF X971 Mo 2,6-Me 2 Ph IMes 2,6-CI 2 PhO - BPh4 X1041 Mo 2,6-Me 2 Ph IMes 2,6-CI 2 PhO ACN PF 6 X1042 Mo 2,6-Me 2 Ph IMes PhO - BF 4 X972 Mo 2,6-Me 2 Ph IMes 2,6-Br 2 PhO - BArF X712 Mo Ad IMes CeFsO ACN BArF X966 W 2,6-CI 2 Ph IMes 2,6-CI 2 PhO PivCN BArF X967 W 2,6-CI 2 Ph IMes CeFsO PivCN BArF X968 W 2,6-CI 2 Ph IMes PhO PivCN BArF X973 W 2,6-CI 2 Ph IMes HMTO PivCN BArF X979 W 2,6-CI 2 Ph IMes 2,6-Br 2 PhO PivCN BArF X965 W 3,5-Me 2 Ph IMes 2,6-CI 2 PhO PivCN BArF X977 W 3,5-Me 2 Ph IMes CeFsO PivCN BArF X980 W 3,5-Me 2 Ph IMes 2,6-Br 2 PhO PivCN BArF X954 W 3,5-Me 2 Ph IMes PhO PivCN BArF or compound of claim 2, wherein the compound is characterized by formula [M(NHC)(=NAr)(=CHCMe 2 C6H5)(Z)(L)]A and wherein the compound is X973. 12. Compound of formula III [M(NHC)(X)(Y)(Z)(L)n]Am III wherein M is Mo or W; NHC is a nitrogen-containing heterocyclic carbene which binds via its carbene carbon atom to M; X is =NR 1 ; Y is an alkylidene or arylidene =CR 2 R 3 ; Z is triflate (TfO); or is halogenide selected from Cl- or Br-; or is -OR 4 , wherein R 4 is C1-10 alkyl or Ce-uaryl, respectively optionally substituted; L is a neutral ligand or an anionic ligand, wherein the anionic ligand is triflate; or is halogenide selected from Cl’ or Br; n is 0, or 1 ; A is a non-coordinating anion; m is 0 or 1 ; wherein R 1 is -C1-10 alkyl or -Ce-uaryl, optionally substituted, respectively; R 2 and R 3 are independently -Ci-walkyl or -Ce-uaryl, optionally substituted, respectively, or -H, wherein not both of R 2 and R 3 are H; wherein in the compound of formula III (i) Z and L are TfO or Br, respectively, and n is 1 and m is 0; or (ii) Z is OR 4 and L is TfO or Br, and n is 1 and m is 0; or (iii) Z is TfO or Br, respectively, L is a neutral ligand, n is 0 or 1 and m is 1 ; and wherein the compound is characterized by formula [M(NHC)(=NAr)(=CHCMe 2 C6H 5 )(Z)(L)] and wherein the compound is selected from compounds X359 to X944 of the following tables; or wherein the compound is characterized by formula [M(NHC)(=NAr)(=CHCMe 2 C6H5)(Z)(L)n]A and wherein the compound is selected from compounds X930 to X963 of the following tables: Catalyst M Ar NHC L Z X359 Mo 2,6-Me 2 Ph IMes TfO TfO X793 Mo 2,6-Me 2 Ph SIMes TfO TfO X457 Mo 2,6-CI 2 Ph IMes TfO TfO X883 Mo 3,5-Me 2 Ph IMes TfO TfO X932 W 2,6-CI 2 Ph IMes Br Br X933 W 2,6-CI 2 Ph SIMes Br Br X959 W 3,5-Me 2 Ph IMes Br Br X942 Mo 2,6-Me 2 Ph IMes TfO PhO X943 Mo 2,6-Me 2 Ph IMes TfO 2-CIPhO X944 Mo 2,6-Me 2 Ph IMes TfO CeFsO Catalyst M Ar NHC Z L A- X930 Mo 2,6-Me 2 Ph IMes TfO - BArF X931 Mo 2,6-Me 2 Ph SIMes TfO - BArF X964 Mo 2,6-Me 2 Ph IMes TfO - BPh 4 X969 Mo 3,5-Me 2 Ph IMes TfO - BArF X955 Mo 2,6-CI 2 Ph IMes TfO - BArF X937 W 2,6-CI 2 Ph IMes Br PivCN BArF X963 W 3,5-Me 2 Ph IMes Br PivCN BArF 3. Method of performing a metathesis reaction, comprising: reacting a compound as defined in any one of claims 1 to 11 with one or more olefins; or reacting a compound of formula III [M(NHC)(X)(Y)(Z)(L)n]Am III wherein M is Mo or W; NHC is a nitrogen-containing heterocyclic carbene which binds via its carbene carbon atom to M; wherein NHC is defined in any one of claims 3 to 5; X is =NR 1 ; Y is an alkylidene or arylidene =CR 2 R 3 ; Z is triflate (TfO); or is halogenide selected from Cl- or Br-; or is -OR 4 , wherein R 4 is C1-10 alkyl or Ce-uaryl, respectively optionally substituted; L is a neutral ligand or an anionic ligand, wherein the anionic ligand is triflate; or is halogenide selected from Cl’ or Br; n is 0 or 1 ; A is a non-coordinating anion; m is 0 or 1 ; wherein R 1 is -C1-10 alkyl or -Ce-uaryl, optionally substituted, respectively; R 2 and R 3 are independently -Ci-walkyl or -Ce-uaryl, optionally substituted, respectively, or -H, wherein not both of R 2 and R 3 are H; wherein in the compound of formula III (iii) Z is TfO or Br, respectively, L is a neutral ligand, n is 0 or 1 and m is 1 ; preferably wherein the compound of formula III is characterized by formula [M(NHC)(=NAr)(=CHCMe 2 C6H5)(Z)(L)n]A and wherein the compound is selected from compounds X930 to X963 , as defined in claim 12; with one or more olefins. 14. Method of claim 13, wherein the metathesis reaction is E-selective. 15. Use of a compound of one of the following formulae , or for an E-selective olefin metathesis reaction; or use of a compound of claim 12 as starting material or intermediate in the synthesis of a compound as defined in any one of claims 1 to 11 .

Description

E-SELECTIVE METATHESIS CATALYSTS FIELD OF THE INVENTION [0001] The present invention relates to cationic molybdenum and tungsten complexes containing a N-heterocyclic carbene (NHC) and preferably a halogen-containing aryloxy ligand. The catalysts are active in olefin metathesis reactions and provide for E-selectivity. BACKGROUND OF THE INVENTION [0002] It is known that most of the olefin metathesis catalysts such as Mo-, W- and Ru- based catalysts provide mixtures of cis/trans isomers when a new olefin with internal double bond is formed. Monoaryloxide pyrrolide (MAP)-type Mo- and W-based Schrock- alkylidenes containing bulky aryloxides were the first to catalyze the formation of cis (Z) C=C double bonds, while the first Ru-based Z-selective catalyst was introduced by Grubbs (Schrock and Grubbs, Nobel prize laureates 2005). Ru-dithiolate complexes also show high Z-selectivity, at relatively high catalyst loading, in the metathesis of terminal double bonds. In case of the cross metathesis of internal olefins it also proved to be stereo-retentive in the metathesis of internal olefins. [0003] M.J. Benedikter et al., “Group 6 metal alkylidene and alkylidyne N-heterocyclic carbene complexes for olefin and alkyne metathesis”, Coordination Chemistry Reviews 415 (2020) 213315 disclose in Table 14 that some of the cationic NHC-containing molybdenum catalysts defined therein and bearing an aryloxy substituent display E- selectivity in the ring opening cross-metathesis (ROCM) of 2,3-disubstituted norbornenes using various substrates, whereas similar catalysts display Z-selectivity. [0004] The authors of this publication propose in Figures 22 and 24 with respect to Table 14 that the steric bulk of the imido ligand in the metallacyclobutane formed by the catalyst and the substrate and/or chelating effects of the substrate with the catalyst may have an influence on the E/Z-ratio in the metathesis product. [0005] WO 2015/162245 discloses N-heterocyclic carbene complexes of metal imido alkylidenes and metal oxo alkylidenes, and the use thereof as catalysts in olefinic metathesis reactions. The catalysts have the formulae I to IV as broadly defined therein, according to which A1 stands for NR2 or PR2, A2 stands for CR2R2', NR2, PR2, 0 or S, A3 stands for N or P, and C stands for a carbene carbon atom, ring B is an unsubstituted or a mono or poly-substituted 5 to 7-membered ring, substituents R2 and R2' stand, inter alia, for a linear or branched Ci -Cw-alkyl group and, if A1 and A2 each stand for NR2 or PR2, are the same or different, M in formulas I, II, III or IV stands for Cr, Mo or W, X1 or X2 in formulas I to IV are the same or different and represent, inter alia, C1-C18 carboxylates and Ci-C -alkoxides, Y is inter alia oxygen or sulphur, Z is inter alia a linear or branched Ci-Cw-alkylenoxy group, and R1 and R1' in formulas I to IV are, inter alia, an aliphatic or aromatic group. [0006] It is e.g. further known from I. Reim at al., “Toward E-selective Olefin Metathesis: Computational Design and Experimental Realization of Ruthenium Thio-lndolate Catalysts”, Topics in Catalysis, Volume 65, pages 448-461 (2022), that E-olefins, with substituents trans-disposed across the double bond, are important structural features in molecular entities ranging from antibiotics and anticancer therapeutics to precision polymers. This reference outlines that to date, metathetical access to E-olefin products can be achieved only via “stereo-retentive” catalysts such as dithiocatechol Ru catalysts, which can transform stereochemically defined E-olefin substrates into E-configured products. The utility of stereo-retentive metathesis is limited by the cost and accessibility of the isomerically pure starting materials required. [0007] Despite the advances in the art, the production of E-olefinic products represents an intellectually and economically attractive challenge. OBJECTS OF THE INVENTION [0008] It is the object of the present invention to provide complexes by means of which the E-selective formation of olefins is achievable in an olefin metathesis reaction taking account of industrial requirements for the application of such catalysts. Industrially feasible, economical procedures require the application of highly active catalysts that allow the use of low catalyst loading, typically below 100 ppm or 0.01 mol%. SUMMARY OF THE INVENTION [0009] This object is achieved with the compounds defined in independent claim 1. Contrary to the teaching of the prior art, the inventors have discovered that in particular halogen-containing aryloxy substituents in cationic molybdenum and tungsten complexes bearing a nitrogen-containing heterocyclic carbene are beneficially E-selective in an olefin metathesis reaction. In a preferred embodiment, the halogen-containing aryloxy substituent is a chlorine-containing aryloxy substituent. [0010] The invention further relates to the molybdenum and tungsten complexes defined in independent claim 2. [00