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US 12,404,221 B2Granted
Methods of arene alkenylation
AssigneeUniversity of Virginia Patent Foundation
InventorsThomas Brent Gunnoe, Xiaofan Jia, Lucas Isaac Frye
Life of this patent
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Abstract
The present disclosure provides for a rhodium-catalyzed oxidative arene alkenylation from arenes and styrenes to prepare stilbene and stilbene derivatives. For example, the present disclosure provides for method of making arenes or substituted arenes, in particular stilbene and stilbene derivatives, from a reaction of an optionally substituted arene and/or optionally substituted styrene. The reaction includes a Rh catalyst or Rh pre-catalyst material and an oxidant, where the Rh catalyst or Rh catalyst formed Rh pre-catalyst material selectively functionalizes CH bond on the arene compound (e.g., benzene or substituted benzene).
Claims24
A method of making a substituted arene, comprising:
- wherein A is a Rh catalyst or Rh pre-catalyst material, wherein the Rh catalyst selectively functionalizes CH bond on the arene compound, wherein B is an oxidant, wherein the Rh catalyst is a composition comprising:
- a rhodium (I) catalyst having one of the following formula:
- L2Rh(L′)X, L3RhX, (L1X1)Rh(L′), [(L)2Rh(μ-X)]2, RhX3, [LnRhy(m-X)m], or (L)nRhm
- wherein L2 is selected from:
- two independent and neutral first ligands each coordinated to Rh(I) through a carbon donor, nitrogen donor, a phosphorus donor, an oxygen donor, or a sulfur donor,
- a neutral bidentate ligand coordinated to Rh(I) through either a carbon donor, nitrogen donor, a phosphorus donor, an oxygen donor, or a sulfur donor, or
- a combination of the neutral first ligand and the neutral bidentate ligand;
- wherein L′ is a neutral second ligand coordinated to Rh(I),
- wherein X is a mono-anionic group, either coordinated to the metal or not,
- wherein L3 is a tridentate first ligand coordinated to Rh(I) in a κ2 or κ3 fashion through a carbon donor, a nitrogen donor, a phosphorus donor, an oxygen donor, a sulfur donor, or a combination thereof,
- wherein L1X1 is a monoanionic bidentate or tridentate second ligand coordinated to Rh(I) in a κ2 or κ3 fashion through a carbon donor, a nitrogen donor, a phosphorus donor, an oxygen donor, a sulfur donor, or a combination thereof,
- wherein L is a neutral, two-electron donating third ligand coordinated to Rh(I), and
- wherein y is 1 to 4, m is 1 to 4 and n is 3(m).
10 more elements
A method of making a substituted arene, comprising:
- wherein A is a Rh catalyst or Rh pre-catalyst material, wherein the Rh catalyst selectively functionalizes CH bond on the benzene compound, wherein B is an oxidant, wherein R51 to R58 are each independently selected from the group consisting of:
- hydrogen, a halide, an alkyl, an alkenyl, a —O—R′, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, —NO2, —C(O)OR′, —CN, SiR′3, and —OR′, wherein each R′ is independently selected from H and an alkyl, wherein the Rh catalyst is a composition comprising:
- a rhodium (I) catalyst having one of the following formula:
- L2Rh(L′)X, L3RhX, (L1X1)Rh(L′), [(L)2Rh(μ-X)]2, RhX3, [LnRhy(m-X)m], or (L)nRhm
- wherein L2 is selected from:
- two independent and neutral first ligands each coordinated to Rh(I) through a carbon donor, nitrogen donor, a phosphorus donor, an oxygen donor, or a sulfur donor,
- a neutral bidentate ligand coordinated to Rh(I) through either a carbon donor, nitrogen donor, a phosphorus donor, an oxygen donor, or a sulfur donor, or
- a combination of the neutral first ligand and the neutral bidentate ligand;
- wherein L′ is a neutral second ligand coordinated to Rh(I),
- wherein X is a mono-anionic group, either coordinated to the metal or not,
- wherein L3 is a tridentate first ligand coordinated to Rh(I) in a κ2 or κ3 fashion through a carbon donor, a nitrogen donor, a phosphorus donor, an oxygen donor, a sulfur donor, or a combination thereof,
- wherein L1X1 is a monoanionic bidentate or tridentate second ligand coordinated to Rh(I) in a κ2 or κ3 fashion through a carbon donor, a nitrogen donor, a phosphorus donor, an oxygen donor, a sulfur donor, or a combination thereof,
- wherein L is a neutral, two-electron donating third ligand coordinated to Rh(I), and
- wherein y is 1 to 4, m is 1 to 4 and n is 3(m).
11 more elements
A method of making a substituted arene, comprising:
- wherein A is a Rh catalyst or Rh pre-catalyst material, wherein the Rh catalyst selectively functionalizes a CH bond in meta and para positions of the substituted benezene relative to the functional group, wherein B is an oxidant,
- wherein R51 to R58 are each independently selected from the group consisting of:
- hydrogen, a halide, an alkyl, an alkenyl, a —O—R′, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, —NO2, —C(O)OR′, —CN, SiR′3, and —OR′, wherein each R′ is independently selected from H and an alkyl,
- wherein R61 to R66 are each independently selected from the group consisting of:
- hydrogen, a halide, an alkyl, an alkenyl, a —O—R″, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, —NO2, —C(O)OR″, —CN, SiR″3 and —OR″, wherein each R″ is independently selected from H and an alkyl,
- wherein the Rh catalyst is a composition comprising:
- a rhodium (I) catalyst having one of the following formula:
- L2Rh(L′)X, L3RhX, (L1X1)Rh(L′), [(L)2Rh(μ-X)]2, RhX3, [LnRhy(m-X)m], or (L)nRhm
- wherein L2 is selected from:
- two independent and neutral first ligands each coordinated to Rh(I) through a carbon donor, nitrogen donor, a phosphorus donor, an oxygen donor, or a sulfur donor,
- a neutral bidentate ligand coordinated to Rh(I) through either a carbon donor, nitrogen donor, a phosphorus donor, an oxygen donor, or a sulfur donor, or
- a combination of the neutral first ligand and the neutral bidentate ligand;
- wherein L′ is a neutral second ligand coordinated to Rh(I),
- wherein X is a mono-anionic group, either coordinated to the metal or not,
- wherein L3 is a tridentate first ligand coordinated to Rh(I) in a κ2 or κ3 fashion through a carbon donor, a nitrogen donor, a phosphorus donor, an oxygen donor, a sulfur donor, or a combination thereof,
- wherein L1X1 is a monoanionic bidentate or tridentate second ligand coordinated to Rh(I) in a κ2 or κ3 fashion through a carbon donor, a nitrogen donor, a phosphorus donor, an oxygen donor, a sulfur donor, or a combination thereof,
- wherein L is a neutral, two-electron donating third ligand coordinated to Rh(I), and
- wherein y is 1 to 4, m is 1 to 4 and n is 3(m).
15 more elements
A method of making a substituted arene, comprising:
- wherein A is a Rh catalyst or Rh pre-catalyst material, wherein the Rh catalyst selectively functionalizes a CH bond in meta and para positions of the substituted benezene relative to the functional group, wherein B is an oxidant,
- wherein R51 to R58 are each independently selected from the group consisting of:
- hydrogen, a halide, an alkyl, an alkenyl, a —O—R′, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, —NO2, —C(O)OR′, —CN, SiR′3, and —OR′, wherein each R′ is independently selected from H and an alkyl,
- wherein R61 to R66 are each independently selected from the group consisting of:
- hydrogen, a halide, an alkyl, an alkenyl, a —O—R″, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, —NO2, —C(O)OR″, —CN, SiR″3 and —OR″, wherein each R″ is independently selected from H and an alkyl,
- wherein the Rh catalyst is a composition comprising:
- a rhodium (I) catalyst having the following structure:
- wherein A1 and A2 are independently selected from the group consisting of:
- a halogen, an acetate group, a sulfur-based ligand, a carbon-based ligand, hydroxyl, alkoxy, oxide, an amido, a phosphide, a phosphido, a nitride, a hydride, a phosphate (PF6), and a borate (BPh4), wherein R21, R22, R23, and R24 are independently selected from the group consisting of:
- an alkyl, an aryl, an acetate, a cyano group, an olefin, an imine, an ether, a nitrile, a ketone, water, a sulfur based ligand, a phosphine, a carbonyl, a phosphite, and a silicon based ligand.
7 more elements
A method of making a substituted arene, comprising:
- wherein A is a Rh catalyst or Rh pre-catalyst material, wherein the Rh catalyst selectively functionalizes a CH bond in meta and para positions of the substituted benezene relative to the functional group, wherein B is an oxidant,
- wherein R51 to R58 are each independently selected from the group consisting of:
- hydrogen, a halide, an alkyl, an alkenyl, a —O—R′, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, —NO2, —C(O)OR′, —CN, SiR′3, and —OR′, wherein each R′ is independently selected from H and an alkyl,
- wherein R61 to R66 are each independently selected from the group consisting of:
- hydrogen, a halide, an alkyl, an alkenyl, a —O—R″, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, —NO2, —C(O)OR″, —CN, SiR″3 and —OR″, wherein each R″ is independently selected from H and an alkyl,
- wherein the Rh catalyst is a composition comprising:
- a rhodium (I) catalyst having the following structure:
- wherein Q1 and Q2 are independently selected from the group consisting of:
- N, O, P, S, Si, and C, wherein Z1 and Z2 are independently selected from the group consisting of:
- a halide, an alkyl, an alkenyl, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, an acetate, a nitrile, a phosphite, a carbonyl, and a carboxylate, optionally, Z1 and Z2 are joined together with a bond to form a 5, 6, or 7-membered ring, wherein R1 and R2 are independently selected from the group consisting of:
- hydrogen, an alkyl, an aryl, an acetate, a cyano group, an olefin, an imine, an ether, a nitrile, a ketone, water, a sulfur based ligand, a phosphine, a carbonyl, a nitrosyl, a silane, and an N-Heterocyclic carbene, wherein R3 and R4 are independently selected from the group consisting of:
- a halide, an alkyl, an alkenyl, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, an acetate, a cyano group, a nitrile, and a phosphite.
9 more elements
A method of making a substituted arene, comprising:
- wherein A is a Rh catalyst or Rh pre-catalyst material, wherein the Rh catalyst selectively functionalizes a CH bond in meta and para positions of the substituted benezene relative to the functional group, wherein B is an oxidant,
- wherein R51 to R58 are each independently selected from the group consisting of:
- hydrogen, a halide, an alkyl, an alkenyl, a —O—R′, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, —NO2, —C(O)OR′, —CN, SiR′3, and —OR′, wherein each R′ is independently selected from H and an alkyl,
- wherein R61 to R66 are each independently selected from the group consisting of:
- hydrogen, a halide, an alkyl, an alkenyl, a —O—R″, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, —NO2, —C(O)OR″, —CN, SiR″3 and —OR″, wherein each R″ is independently selected from H and an alkyl,
- wherein the Rh catalyst is a composition comprising:
- a rhodium (I) catalyst having the following structure:
- wherein Q3, Q4, and Q5 are independently selected from the group consisting of:
- N, O, P, S, and Si, wherein Z3 and Z4 are independently selected from the group consisting of:
- a halide, an alkyl, an alkenyl, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, an acetate, a cyano group, a carbonyl, and a silyl group, optionally, Z3 and Z4 are joined together with a bond to form a 5, 6, or 7-membered ring, wherein R11 and R12 are independently selected from the group consisting of:
- hydrogen, an alkyl, an aryl, an acetate, a cyano group, an olefin, an imine, an ether, a nitrile, a ketone, water, a sulfur based ligand, a phosphine, a silyl group, and an N-heterocyclic carbene, wherein R10, R13, R14 R15, and R16 are independently selected from the group consisting of:
- a halide, an alkyl, an alkenyl, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, an acetate, a cyano group, a nitrile, and a phosphite wherein, optionally, R15 and R14, R14 and R11, or R11, R14, and R15 are joined together with a bond(s) to form a 5, 6, or 7-membered ring, wherein, optionally, R16 and R13, R13 and R12, or R12, R13, and R16 are joined together with a bond(s) to form a 5, 6, or 7-membered ring.
9 more elements
A method of making a substituted arene, comprising:
- wherein A is a Rh catalyst or Rh pre-catalyst material, wherein the Rh catalyst selectively functionalizes a CH bond in meta and para positions of the substituted benezene relative to the functional group, wherein B is an oxidant,
- wherein R51 to R58 are each independently selected from the group consisting of:
- hydrogen, a halide, an alkyl, an alkenyl, a —O—R′, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, —NO2, —C(O)OR′, —CN, SiR′3, and —OR′, wherein each R′ is independently selected from H and an alkyl,
- wherein R61 to R66 are each independently selected from the group consisting of:
- hydrogen, a halide, an alkyl, an alkenyl, a —O—R″, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, —NO2, —C(O)OR″, —CN, SiR″3 and —OR″, wherein each R″ is independently selected from H and an alkyl,
- wherein the Rh pre-catalyst material comprises Rh nanoparticles on a support or single atom Rh material on the support.
3 more elements
A method of making a substituted arene, comprising:
- wherein A is a Rh catalyst or Rh pre-catalyst material, wherein the Rh catalyst selectively functionalizes CH bond on the arene compound, wherein B is an oxidant, wherein the Rh catalyst is a composition comprising:
- a rhodium (I) catalyst having the following structure:
- wherein A1 and A2 are independently selected from the group consisting of:
- a halogen, an acetate group, a sulfur-based ligand, a carbon-based ligand, hydroxyl, alkoxy, oxide, an amido, a phosphide, a phosphido, a nitride, a hydride, a phosphate (PF6), and a borate (BPh4), wherein R21, R22, R23, and R24 are independently selected from the group consisting of:
- an alkyl, an aryl, an acetate, a cyano group, an olefin, an imine, an ether, a nitrile, a ketone, water, a sulfur based ligand, a phosphine, a carbonyl, a phosphite, and a silicon based ligand.
2 more elements
A method of making a substituted arene, comprising:
- wherein A is a Rh catalyst or Rh pre-catalyst material, wherein the Rh catalyst selectively functionalizes CH bond on the arene compound, wherein B is an oxidant, wherein the Rh catalyst is a composition comprising:
- a rhodium (I) catalyst having the following structure:
- wherein Q1 and Q2 are independently selected from the group consisting of:
- N, O, P, S, Si, and C, wherein Z1 and Z2 are independently selected from the group consisting of:
- a halide, an alkyl, an alkenyl, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, an acetate, a nitrile, a phosphite, a carbonyl, and a carboxylate, optionally, Z1 and Z2 are joined together with a bond to form a 5, 6, or 7-membered ring, wherein R1 and R2 are independently selected from the group consisting of:
- hydrogen, an alkyl, an aryl, an acetate, a cyano group, an olefin, an imine, an ether, a nitrile, a ketone, water, a sulfur based ligand, a phosphine, a carbonyl, a nitrosyl, a silane, and an N-Heterocyclic carbene, wherein R3 and R4 are independently selected from the group consisting of:
- a halide, an alkyl, an alkenyl, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, an acetate, a cyano group, a nitrile, and a phosphite.
4 more elements
A method of making a substituted arene, comprising:
- wherein A is a Rh catalyst or Rh pre-catalyst material, wherein the Rh catalyst selectively functionalizes CH bond on the arene compound, wherein B is an oxidant, wherein the Rh catalyst is a composition comprising:
- a rhodium (I) catalyst having the following structure:
- wherein Q3, Q4, and Q5 are independently selected from the group consisting of:
- N, O, P, S, and Si, wherein Z3 and Z4 are independently selected from the group consisting of:
- a halide, an alkyl, an alkenyl, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, an acetate, a cyano group, a carbonyl, and a silyl group, optionally, Z3 and Z4 are joined together with a bond to form a 5, 6, or 7-membered ring, wherein R11 and R12 are independently selected from the group consisting of:
- hydrogen, an alkyl, an aryl, an acetate, a cyano group, an olefin, an imine, an ether, a nitrile, a ketone, water, a sulfur based ligand, a phosphine, a silyl group, and an N-heterocyclic carbene, wherein R10, R13, R14 R15, and R16 are independently selected from the group consisting of:
- a halide, an alkyl, an alkenyl, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, an acetate, a cyano group, a nitrile, and a phosphite wherein, optionally, R15 and R14, R14 and R11, or R11, R14, and R15 are joined together with a bond(s) to form a 5, 6, or 7-membered ring, wherein, optionally, R16 and R13, R13 and R12, or R12, R13, and R16 are joined together with a bond(s) to form a 5, 6, or 7-membered ring.
4 more elements
A method of making a substituted arene, comprising:
- wherein A is a Rh catalyst or Rh pre-catalyst material, wherein the Rh catalyst selectively functionalizes CH bond on the arene compound, wherein B is an oxidant, wherein the Rh pre-catalyst material comprises Rh nanoparticles on a support or single atom Rh material on the support.
A method of making a substituted arene, comprising:
- wherein A is a Rh catalyst or Rh pre-catalyst material, wherein the Rh catalyst selectively functionalizes CH bond on the benzene compound, wherein B is an oxidant, wherein R51 to R58 are each independently selected from the group consisting of:
- hydrogen, a halide, an alkyl, an alkenyl, a —O—R′, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, —NO2, —C(O)OR′, —CN, SiR′3, and —OR′, wherein each R′ is independently selected from H and an alkyl, wherein the Rh catalyst is a composition comprising:
- a rhodium (I) catalyst having the following structure:
- wherein A1 and A2 are independently selected from the group consisting of:
- a halogen, an acetate group, a sulfur-based ligand, a carbon-based ligand, hydroxyl, alkoxy, oxide, an amido, a phosphide, a phosphido, a nitride, a hydride, a phosphate (PF6), and a borate (BPh4), wherein R21, R22, R23, and R24 are independently selected from the group consisting of:
- an alkyl, an aryl, an acetate, a cyano group, an olefin, an imine, an ether, a nitrile, a ketone, water, a sulfur based ligand, a phosphine, a carbonyl, a phosphite, and a silicon based ligand.
3 more elements
A method of making a substituted arene, comprising:
- wherein A is a Rh catalyst or Rh pre-catalyst material, wherein the Rh catalyst selectively functionalizes CH bond on the benzene compound, wherein B is an oxidant, wherein R51 to R58 are each independently selected from the group consisting of:
- hydrogen, a halide, an alkyl, an alkenyl, a —O—R′, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, —NO2, —C(O)OR′, —CN, SiR′3, and —OR′, wherein each R′ is independently selected from H and an alkyl, wherein the Rh catalyst is a composition comprising:
- a rhodium (I) catalyst having the following structure:
- wherein Q1 and Q2 are independently selected from the group consisting of:
- N, O, P, S, Si, and C, wherein Z1 and Z2 are independently selected from the group consisting of:
- a halide, an alkyl, an alkenyl, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, an acetate, a nitrile, a phosphite, a carbonyl, and a carboxylate, optionally, Z1 and Z2 are joined together with a bond to form a 5, 6, or 7-membered ring, wherein R1 and R2 are independently selected from the group consisting of:
- hydrogen, an alkyl, an aryl, an acetate, a cyano group, an olefin, an imine, an ether, a nitrile, a ketone, water, a sulfur based ligand, a phosphine, a carbonyl, a nitrosyl, a silane, and an N-Heterocyclic carbene, wherein R3 and R4 are independently selected from the group consisting of:
- a halide, an alkyl, an alkenyl, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, an acetate, a cyano group, a nitrile, and a phosphite.
5 more elements
A method of making a substituted arene, comprising:
- wherein A is a Rh catalyst or Rh pre-catalyst material, wherein the Rh catalyst selectively functionalizes CH bond on the benzene compound, wherein B is an oxidant, wherein R51 to R58 are each independently selected from the group consisting of:
- hydrogen, a halide, an alkyl, an alkenyl, a —O—R′, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, —NO2, —C(O)OR′, —CN, SiR′3, and —OR′, wherein each R′ is independently selected from H and an alkyl, wherein the Rh catalyst is a composition comprising:
- a rhodium (I) catalyst having the following structure:
- wherein Q3, Q4, and Q5 are independently selected from the group consisting of:
- N, O, P, S, and Si, wherein Z3 and Z4 are independently selected from the group consisting of:
- a halide, an alkyl, an alkenyl, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, an acetate, a cyano group, a carbonyl, and a silyl group, optionally, Z3 and Z4 are joined together with a bond to form a 5, 6, or 7-membered ring, wherein R11 and R12 are independently selected from the group consisting of:
- hydrogen, an alkyl, an aryl, an acetate, a cyano group, an olefin, an imine, an ether, a nitrile, a ketone, water, a sulfur based ligand, a phosphine, a silyl group, and an N-heterocyclic carbene, wherein R10, R13, R14 R15, and R16 are independently selected from the group consisting of:
- a halide, an alkyl, an alkenyl, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, an acetate, a cyano group, a nitrile, and a phosphite wherein, optionally, R15 and R14, R14 and R11, or R11, R14, and R15 are joined together with a bond(s) to form a 5, 6, or 7-membered ring, wherein, optionally, R16 and R13, R13 and R12, or R12, R13, and R16 are joined together with a bond(s) to form a 5, 6, or 7-membered ring.
5 more elements
A method of making a substituted arene, comprising:
- wherein A is a Rh catalyst or Rh pre-catalyst material, wherein the Rh catalyst selectively functionalizes CH bond on the benzene compound, wherein B is an oxidant, wherein R51 to R58 are each independently selected from the group consisting of:
- hydrogen, a halide, an alkyl, an alkenyl, a —O—R′, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, —NO2, —C(O)OR′, —CN, SiR′3, and —OR′, wherein each R′ is independently selected from H and an alkyl, wherein the Rh pre-catalyst material comprises a Rh nanoparticles on a support or single atom Rh material on the support.
Dependencies are inferred from the claim text.