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EP-4508056-B1 - INDOLE-FUNCTIONALIZED BISPHOSPHORAMIDITES, METHODS FOR THE PREPARATION THEREOF, AND RHODIUM-LIGAND COMPLEX

EP4508056B1EP 4508056 B1EP4508056 B1EP 4508056B1EP-4508056-B1

Inventors

  • BISWAS, Souvagya
  • BRAMMER, MICHAEL A.
  • SPINNEY, Heather
  • FROESE, Robert
  • BERNALES, Varinia
  • FIGUEROA, RUTH

Dates

Publication Date
20260506
Application Date
20230413

Claims (10)

  1. An indole-functionalized bisphosphoramidite having a formula selected from the group consisting of: and where R 1 -R 42 are each independently selected from H, a hydrocarbyl group, a heteroaryl group, a halogen atom, or a heterocarbyl group, with the proviso that at least one of R 35 -R 42 is not H; each of Y 1 to Y 12 is an independently selected indole group of formula (I): where each of R 43 -R 47 is an independently selected atom or group selected from H, alkyl, aryl, heteroaryl, alkoxy, acyl, carboxyl, carboxylate, cyano, -SO 3 H, sulfonate, amino, trifluoromethyl, halogen, a group of formula (II) below, and combinations thereof; with the provisos that i) two or more of R 44 -R 47 may optionally be bonded together to give one or more cyclic moieties, and ii) in at least one of each of Y 1 -Y 4 , Y 5 -Y 8 , and Y 9 -Y 12 , either a) at least one of R 43 -R 47 has formula (II) where each of R 48 -R 52 is an independently selected atom or group selected from H, alkyl, aryl, and alkoxy; or b) two or more of R 44 -R 47 are bonded together to give one or more cyclic moieties; and iii) when the indole-functionalized bisphosphoramidite has the formula C1), at least one of R 44 -R 46 of at least one of Y 1 -Y 4 has formula (II).
  2. The indole-functionalized bisphosphoramidite of claim 1, where formula (II) is selected from the group consisting of:
  3. The indole-functionalized bisphosphoramidite of claim 1 or 2, where in formula C1) each of R 1 -R 20 is H; in formula C2) each of R 21 -R 34 is H, and in formula C3) each of R 35 and R 42 is H, and each of R 36 -R 41 is methyl.
  4. The indole-functionalized bisphosphoramidite of claim 1 or 2, wherein proviso (ii)(a) is true, and wherein at least one of R 44 -R 46 has formula (II).
  5. The indole-functionalized bisphosphoramidite of claim 1 or 2, wherein proviso (ii)(a) is true, and wherein one of R 45 and/or R 46 has formula (II).
  6. The indole-functionalized bisphosphoramidite of claim 1, wherein the indole-functionalized bisphosphoramidite is selected from the group consisting of: L1) 2,2'-bis((bis(6-mesityl-1H-indol-1-yl)phosphaneyl)oxy)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthalene; L2) 2,2'-bis((bis(6-(3,5-dimethylphenyl)-1H-indol-1-yl)phosphaneyl)oxy)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthalene; L3) 2,2'-bis((bis(6-(3,5-di-tert-butylphenyl)-1H-indol-1-yl)phosphaneyl)oxy)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthalene; L4) 2,2'-bis((bis(6-([1,1':3',1"-terphenyl]-5'-yl)-1H-indol-1-yl)phosphaneyl)oxy)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthalene; L5) 2,2'-bis((bis(6-([1,1':3',1"-terphenyl]-5'-yl)-1H-indol-1-yl)phosphaneyl)oxy)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthalene; L6) 2,2'-bis((bis(6-(4-(tert-butyl)phenyl)-1H-indol-1-yl)phosphaneyl)oxy)-5,5',6,6',7,1',8,8'-octahydro-1,1'-binaphthalene; L7) 2,2'-bis((bis(6-(4-methoxyphenyl)-1H-indol-1-yl)phosphaneyl)oxy)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthalene; L8) 2,2'-bis((bis(5-(3,5-di-tert-butylphenyl)-1H-indol-1-yl)phosphaneyl)oxy)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthalene; L9) 2,2'-bis((bis(4-(3,5-di-tert-butylphenyl)-1H-indol-1-yl)phosphaneyl)oxy)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthalene; L10) 1,1',1",1‴-(((4,4',5,5',6,6'-hexamethyl-[1,1'-biphenyl]-2,2'-diyl)bis(oxy))bis(phosphanetriyl))tetrakis(6-(3,5-di-tert-butylphenyl)-1H-indole); L11) 4,4'-bis((bis(6-(3,5-di-tert-butylphenyl)-1H-indol-1-yl)phosphaneyl)oxy)-1,1',3,3'-tetrahydro-2,2'-spirobi[indene]; L12) 2,2'-bis(((7,8-dihydrocyclopenta[g]indol-1(6H)-yl)(1H-indol-1-yl)phosphaneyl)oxy)-5,5',6,6',7,1',8,8'-octahydro-1,1'-binaphthalene; and L13) 2,2'-bis((bis(6-(3,5-di-tert-butylphenyl)-3-methyl-1H-indol-1-yl)phosphaneyl)oxy)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthalene.
  7. A method for preparing a rhodium-ligand complex, said method comprising: 1) combining starting materials comprising (I) a rhodium catalyst precursor, and (II) the indole-functionalized bisphosphoramidite of claims 1 or 2, and optionally (III) a solvent.
  8. The method of claim 7, where the rhodium catalyst precursor is selected from the group consisting of Rh 2 O 3 , Rh 4 (CO) 12 , Rh 6 (CO) 16 , and Rh(NO 3 ) 3 .
  9. The method of claim 7 or 8, where the rhodium-ligand complex has a molar ratio of ligand/Rh of 1/1 to 10/1.
  10. A rhodium-ligand complex prepared by the method of claim 7.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and all advantages of U.S. Provisional Patent Application No. 63/330,571 filed on 13 April 2022. TECHNICAL FIELD An indole-functionalized bisphosphoramidite having a certain formula is disclosed. The indole-functionalized bisphosphoramidite is suitable for use as a ligand, particularly for preparing a rhodium-ligand complex. A method of preparing a rhodium-ligand complex with the indole-functionalized bisphosphoramidite is also disclosed. BACKGROUND Aldehydes are important intermediates in the synthesis of other functionalized materials like alcohols, carboxylic acids, and amines. The introduction of aldehyde functionality into olefins, especially via a continuous process, is important in many industries. The hydroformylation of olefins to prepare aldehydes is highly dependent on catalyst selection, both in terms of aldehyde selectivity (as linear aldehydes are generally preferred over branched aldehydes), production rate, and catalyst stability. Many conventional catalysts utilized in hydroformylation of olefins, even if having desirable selectivity, have poor stability that deactivate over time, which is undesirable. CN 112 851 708 A discloses a method for preparing olefine aldehyde by catalyzing terminal alkyne or terminal conjugated eneyne. BRIEF SUMMARY An indole-functionalized bisphosphoramidite is disclosed. The indole-functionalized bisphosphoramidite has a formula selected from the group consisting of C1), C2), or C3): or or In formulas C1)-C3), R1-R42 are each independently selected from H, a hydrocarbyl group, a heteroaryl group, a halogen atom, or a heterocarbyl group, with the proviso that at least one of R35-R42 is not H. Each of Y1 to Y12 is an independently selected indole group of formula (I): where each of R43-R47 is an independently selected atom or group selected from H, alkyl, aryl, heteroaryl, alkoxy, acyl, carboxyl, carboxylate, cyano, -SO3H, sulfonate, amino, trifluoromethyl, halogen, a group of formula (II) below, and combinations thereof. In the indole-functionalized bisphosphoramidite, the following provisos apply: i) two or more of R44-R47 may optionally be bonded together to give one or more cyclic moieties, andii) in at least one of each of Y1-Y4, Y5-Y8, and Y9-Y12, either a) at least one of R43-R47 has formula (II) where each of R48-R52 is an independently selected atom or group selected from H, alkyl, aryl, and alkoxy; orb) two or more of R44-R47 are bonded together to give one or more cyclic moieties; andiii) when the indole-functionalized bisphosphoramidite has the formula C1), at least one of R44-R46 of at least one of Y1-Y4 has formula (II). A method for preparing a rhodium-ligand complex is also disclosed. The method comprises 1) combining starting materials comprising: (I) a rhodium catalyst precursor, and (II) the indole-functionalized bisphosphoramidite; and optionally (III) a solvent. DETAILED DESCRIPTION An indole-functionalized bisphosphoramidite is disclosed. The indole-functionalized bisphosphoramidite has a formula selected from the group consisting of C1), C2), or C3): or or In formulas C1)-C3), R1-R42 are each independently selected from H, a hydrocarbyl group, a heteroaryl group, a halogen atom, or a heterocarbyl group, with the proviso that at least one of R35-R42 is not H. Because at least one of R35-R42 is not H. at least one of R35-R42 is a hydrocarbyl group, a heteroaryl group, a halogen atom, or a heterocarbyl group. Suitable hydrocarbyl groups for R1-R42 may independently be linear, branched, cyclic, or combinations thereof. Cyclic hydrocarbyl groups encompass aryl groups as well as saturated or non-conjugated cyclic groups. Cyclic hydrocarbyl groups may be monocyclic or polycyclic. Linear and branched hydrocarbyl groups may independently be saturated or unsaturated. One example of a combination of a linear and cyclic hydrocarbyl group is an aralkyl group. By "substituted," it is meant that one or more hydrogen atoms may be replaced with atoms other than hydrogen (e.g. a halogen atom, such as chlorine, fluorine, bromine, etc.). Suitable alkyl groups are exemplified by, but not limited to, methyl, ethyl, propyl (e.g., iso-propyl and/or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and/or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and/or tert-pentyl), hexyl, as well as branched saturated hydrocarbon groups of 6 carbon atoms. Suitable aryl groups are exemplified by, but not limited to, phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethyl phenyl. Suitable alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, and cyclohexenyl groups. Suitable monovalent halogenated hydrocarbon groups include, but are not limited to, a halogenated alkyl group of 1 to 6 carbon atoms, or a halogenated aryl group of 6 to 10 carbon atoms. Suitable halogenated alkyl groups are exemplified by, but not limited to, the alkyl groups d