# US 10,118,169 B2 · Chiral ligand-based metal-organic frameworks for broad-scope asymmetric catalysis

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- Number: US 10,118,169 B2
- Document ID: US10118169B2
- Status: Granted
- Kind: B2
- Application number: 15/129,851
- Filed: 2015-03-30
- Published: 2017-06-22
- Granted: 2018-11-06
- Earliest claimed: 2014-03-28
- Assignees: The University of Chicago; The University of North Carolina at Chapel Hill
- Applicants: The University of Chicago; The University of North Carolina at Chapel Hill
- Inventors: Wenbin Lin; Joseph M. Falkowski; Takahiro Sawano
- Web page: https://patentgrep.com/patent/US10118169B2

## CPC

- B01J 31/1691: {Coordination polymers, e.g. metal-organic frameworks [MOF] (preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F)}
- B01J 31/1805: {the ligands containing nitrogen}
- B01J 31/182: {comprising aliphatic or saturated rings}
- B01J 31/2409: {with more than one complexing phosphine-P atom}
- B01J 31/2433: {comprising aliphatic or saturated rings}
- B01J 31/2447: {and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring}
- C07C 29/44: increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon double or triple bond (C07C29/16 takes precedence)
- C07C 41/09: by dehydration of compounds containing hydroxy groups
- C07C 45/69: by addition to carbon-to-carbon double or triple bonds
- C07C 67/303: by hydrogenation of unsaturated carbon-to-carbon bonds
- C07C 227/04: Formation of amino groups in compounds containing carboxyl groups
- C07C 231/02: from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
- C07D 307/93: condensed with a ring other than six-membered
- B01J 2531/0205: Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
- B01J 2531/0263: Planar chiral ligands, e.g. derived from donor-substituted paracyclophanes and metallocenes or from substituted arenes
- B01J 2531/0266: Axially chiral or atropisomeric ligands, e.g. bulky biaryls such as donor-substituted binaphthalenes, e.g. "BINAP" or "BINOL"
- B01J 2531/822: Rhodium
- C07C 2602/44: the bicyclo ring system containing eight carbon atoms
- Y02P 20/54: using solvents, e.g. supercritical solvents or ionic liquids
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Metal-organic framework (MOFs) compositions based on chiral phosphine-, chiral oxazoline-, chiral pyridine-, and chiral diene-derived organic bridging ligands were synthesized and then post-synthetically metalated with metal precursors such as Ru and Rh complexes. The metal complexes could also be directly incorporated into the MOFs. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations, including the addition of arylboronic acids to α,β-unsaturated ketones and alkimines, the hydrogenation of substituted alkene and carbonyl compounds, and cyclization reactions. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.

## Claims

### Claim 1

An asymmetric heterogeneous catalyst comprising a crystalline and porous metal-organic framework (MOF), wherein said crystalline and porous MOF comprises periodic repeats of a coordination complex comprising (a) a metal-based secondary building unit (SBU), wherein said metal-based SBU comprises a first metal, and (b) a chiral bridging ligand, wherein said chiral bridging ligand is coordinatively bonded to more than one SBU, wherein said chiral bridging ligand is further complexed to a second metal to provide a catalytic moiety, and wherein said chiral bridging ligand is a dicarboxylate-substituted chiral bisphosphine or a dicarboxylate-substituted chiral bicyclo[2.2.2]octane-2,5-diene.

### Claim 2 (depends on 1)

The catalyst of claim 1, wherein said catalyst is prepared by providing the chiral bridging ligand, contacting the chiral bridging ligand with a first metal source to obtain a MOF, and further comprising contacting the MOF with a second metal source to metalate the organic bridging ligand.

### Claim 3 (depends on 1)

The catalyst of claim 1, further comprising a non-chiral bridging ligand, optionally wherein the non-chiral bridging ligand is 4,4′((2-nitro-[1,1′-biphenyl]-4,4′-diyl)bis(ethyne-2,1-diyl))dibenzoic acid or 4,4′-(2-nitro[1,1′-biphenyl])bisbenzoic acid.

### Claim 4 (depends on 1)

The catalyst of claim 1, wherein the SBU is a Zr-oxo cluster.

### Claim 5 (depends on 1)

The catalyst of claim 1, wherein the second metal is Ru or Rh.

### Claim 6 (depends on 1)

A method for preparing the asymmetric heterogeneous catalyst of claim 1, said method comprising providing the chiral bridging ligand; contacting the chiral bridging ligand with a first metal source to obtain the crystalline and porous MOF; and contacting the crystalline and porous MOF with a second metal source to metalate the chiral bridging ligand.

### Claim 7 (depends on 6)

The method of claim 6, wherein the first metal source is ZrCl4.

### Claim 8 (depends on 6)

The method of claim 6, wherein the second metal source is Ru(cyclooctadiene)(2-Me-allyl)2, Rh(norbornadiene)2BF4, [RhCl(C2H2)2]2, or Rh(acetylacetonate)(C2H4)2.

### Claim 9 (depends on 6)

The method of claim 6, wherein the chiral bridging ligand and the first metal source are contacted in a solvent or mixture of solvents selected based on solvent molecule size, such that the sizes and/or shapes of internal pores, cavities, and/or open channels in the crystalline and porous MOF can be tailored to enhance catalytic activity and selectivity.

### Claim 10 (depends on 9)

The method of claim 9, wherein the solvent comprises dimethylformamide (DMF).

### Claim 11 (depends on 1)

A method for preparing an asymmetric compound comprising contacting a substrate capable of forming an asymmetric product by an asymmetric reaction with an asymmetric heterogeneous catalyst of claim 1.

### Claim 12 (depends on 11)

The method of claim 11, wherein the asymmetric reaction is selected from the group consisting of hydrogenation; isomerization, optionally the isomerization of an allylamine, an allyl alcohol, or an α,β-unsaturated ketone; allylic substitution; a coupling reaction, optionally wherein the coupling reaction is a Buchwald-Hartwig amination, an intramolecular Heck reaction, or an intermolecular Heck reaction; conjugate addition, optionally wherein the conjugate addition is a Michael addition or an azo-Michael addition; an aldol reaction; a Mannich-type reaction; nucleophilic addition, optionally wherein the nucleophilic addition is to a carbonyl or imine group and/or wherein the nucleophilic addition is a cyanation, a propargylation, an allylation, a dienylation, an arylation, an alkenylation, or an alkylation; hydroformylation; hydroacylation; hydroboration; hydroamination; intra- or intermolecular hydrosilylation; an α-substitution reaction, optionally wherein the α-substitution reaction is a protonation, a fluorination, an amination, an arylation, or an orthoester alkylation; an ene reaction; a Diels-Alder reaction; a Pauson-Khand reaction; an Alder-Ene reaction, an enyne intramolecular cyclization; a [2+2+2] cycloaddition; a [3+2] cycloaddition; and a ring-opening reaction.

### Claim 13 (depends on 11)

The method of claim 11, wherein the asymmetric reaction is performed in the presence or absence of a solvent, optionally wherein a solvent is present, further optionally wherein the solvent is supercritical carbon dioxide.

### Claim 14 (depends on 11)

The method of claim 11, wherein the asymmetric reaction is performed in a flow reactor.

### Claim 15 (depends on 11)

The method of claim 11, wherein the asymmetric reaction is selected from the group consisting of 1,4-addition of an arylboronic acid to an α,β-unsaturated ketone; 1,2-addition of trimethylaluminum to an α,β-unsaturated ketone, 1,2-addition of an arylboronic acid to an aldimine, hydrogenation of a β-keto ester, hydrogenation of a substituted alkene, reductive cyclization of a 1,6-enyne, an Alder-Ene reaction, and a Pauson-Khand reaction.

### Claim 16 (depends on 11)

The method of claim 11, wherein the contacting is performed by contacting the substrate with about 3 mole percentage or less of the catalyst as compared to the substrate.

### Claim 17 (depends on 1)

A method of preparing a compound, wherein the method comprises using a catalyst of claim 1 to catalyze a multi-step reaction or to catalyze sequential reactions.

### Claim 18 (depends on 1)

A method of preparing a compound, wherein the method comprises using a plurality of catalysts of claim 1 to catalyze sequential reactions or to catalyze a multi-step reaction.