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WO2023248253A1 - Nouvel échafaudage de ligand (py-pyri) pour la méta borylation de dérivés de phénol - Google Patents

Nouvel échafaudage de ligand (py-pyri) pour la méta borylation de dérivés de phénol Download PDF

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Publication number
WO2023248253A1
WO2023248253A1 PCT/IN2023/050608 IN2023050608W WO2023248253A1 WO 2023248253 A1 WO2023248253 A1 WO 2023248253A1 IN 2023050608 W IN2023050608 W IN 2023050608W WO 2023248253 A1 WO2023248253 A1 WO 2023248253A1
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Prior art keywords
borylation
catalyst
meta
group
ome
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Inventor
Saikat Guria
Mirja Md Mahamudul Hassan
Sayan Dey
Buddhadeb Chattopadhyay
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Centre Of Biomedical Research
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Centre Of Biomedical Research
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0033—Iridium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/46—C-H or C-C activation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/827—Iridium

Definitions

  • This new ligand framework is highly reactive and afforded meta selective borylation of various substituted TIPS protected phenol and borylation reaction not affected by the substituents steric crowding. 4- Substituents arenes gave meta borylated product under the developed reaction conditions which was rarely gave meta borylation with other catalytic borylation conditions. Very few methods have been developed for the meta functionalization of phenol, but the meta borylation is not developed yet.
  • This invention provides an access to functionalize the meta positions of TIPS protected phenol with the new pyridine-pyridone ligand framework with [Ir(cod)OMe]2 and Ehpi as a borylating agent in cyclohexane solvent.
  • Indian patent application no. 202011035905 is related to a process of iridium- catalyzed meta- C-H activation and borylation of diverse range of anilines and their derivative.
  • the N-H proton of aniline is protected with either -SO2CF3, -SO2CH3, - COCH3 or -COCF3 group and the second N-H proton is protected with alkyl chain.
  • the modification of aniline substrate and combination of [Ir(cod)(OMe)]2, 1,10- phenanthroline ligand and borylating reagent fhpi give the selective meta- borylated product in nonpolar cyclohexane solvent at 40-80 °C.
  • Indian patent no. 399886 is related to a process of iridium-catalyzed ortho C-H activation and borylation of a diverse class of aromatic and heteroaromatic molecules in the presence of fhpi as the borylating agent, non-reacting solvents like hexane, tetrahydrofuran (THF) at temperatures between 40 °C to 100 °C.
  • fhpi as the borylating agent
  • non-reacting solvents like hexane, tetrahydrofuran (THF) at temperatures between 40 °C to 100 °C.
  • PCT publication no. WO2015195680 discloses a method for preparing a borylated aromatic compound by contacting an aromatic substrate with a catalytic cobalt complex and a borylation reagent.
  • the catalytic cobalt complex can be any suitable cobalt(I) or cobalt(II) complex that can catalyze the C-H activation-borylation of the aromatic substrate.
  • Boebel, Timothy et al. discloses silyl-directed, iridium-catalyzed ort/20-borylation of arenes. By this method, arenes containing hydrosilyl substituents on an atom attached to the arene ring undergo borylation at the position ortho to the hydrosilyl group.
  • Literature precedence revealed that common structural motif for this O-Si interaction is the amide skeleton, where filled p-orbital of oxygen atom can interact with the vacant d-orbital of tetracoordinated silicon atom consisting of at least one electronegative atom.
  • the role of this electronegative atom is to make silicon more electropositive by developing a partial positive charge on the silicon atom.
  • the present invention discloses a novel ligand core for the remote borylation of arenes and heteroarenes which is found to be more superior than the reported bipyridine based bidentate ligands in iridium-catalyzed C-H borylation.
  • the novel ligand of the invention comprises a 'R 1 group.
  • Ligand 'Lx' is represented as LI and L2.
  • the present invention discloses a catalyst (catalyst-X) for the remote borylation of TIPS protected phenol which is found to be very active and air stable catalyst.
  • the novel catalyst of the invention comprises a 'R' group and synthesized from LI and L2 and [Ir(cod)OMe]2.
  • R 4 independently selected from the group consisting of -H groups.
  • the present invention discloses a novel ligand core for the remote borylation of arenes and heteroarenes which is found to be more superior than the reported bipyridine based bidentate ligands in iridium-catalyzed C-H borylation.
  • the ligand used for iridium-catalyzed C-H borylation is 4'-(tert-butyl)-[2,2'- bipyridin]-6-ol (L2).
  • the present invention provides the process for meta borylation of TIPS protected phenol
  • R 1 independently selected from the group consisting of -H,-Me, -Cl, -CONEt2, -Cy, CF3, -CN, -Bpin, -I, -"pent, CF3, -OMe groups;
  • R 4 independently selected from the group consisting of -H groups.
  • the present invention discloses a catalyst (catalyst-X) for the remote borylation of TIPS protected phenol which is found to be very active and air stable catalyst.
  • the novel catalyst of the invention comprises a 'R' group and synthesized from LI and L2 and [Ir(cod)OMe]2.
  • B 2 pin 2 as a borylating reagent are used for the meta-borylation of TIPS protected phenol in non-reacting solvent cyclohexane (CyH) as shown below:
  • the present invention provides the process for meta borylation of TIPS protected phenol
  • R 1 independently selected from the group consisting of -H,-Me, -Cl, -CONEt2, -Cy, CF3, -CN, -Bpin, -I, -"pent, CF3, -OMe groups;
  • R 4 independently selected from the group consisting of -H groups.
  • tributyltin chloride (4 mL, 15 mmol, 1.5 equiv.) was added through the syringe, and the reaction mixture was stirred additional 1 h at -78 °C and then at room temperature for 12 h. Then a saturated solution of NH4CI poured into the reaction mixture and stirred for 15 minutes. The mixture was extracted with ethylacetate (3 x 50 mL) and dried over Na2SO4. Finally, the solvent was evaporated under reduced pressure to get 4-methyl-2-(tributylstannyl)pyridine as a yellowish gummy liquid which was pure enough to use directly for the next step without further purifications.
  • Substrate 1 of Table 1 eta-Borylation of Triisopropyl(phenoxy)silane:
  • Substrate 2 of Table 1 eta-Borylation of Triisopropyl(o-tolyloxy)silane:
  • Substrate 9 of Table 1 eta-Borylation of (2-iodophenoxy)triisopropylsilane: In an argon-filled glove box, a 5.0 mL Wheaton microreactor was charged with [Ir(cod)OMe]2 (4.97 mg, 1.5 mol%), B2pin2 (127.0 mg, 1.0 equiv.), ligand L2 (3.4 mg, 3.0 mol%), HBpin (3.2 mg, 5.0 mol%) and dry cyclohexane (1.0 mL) were added sequentially. The reaction mixture was stirred for 2 minutes at room temperature and then (2-iodophenoxy)triisopropylsilane (0.5 mmol, 188 mg) was added.
  • the microreactor was capped with a Teflon pressure cap and placed into aluminum block at room temperature and stirred for 24 h. After completion (judged by GC-MS), CyH was removed under reduced pressure and chromatographic separation with silica gel (2% EtOAc in hexane as eluent) gave 205.8 mg (82%) of the meto-borylated product as a colourless gummy liquid.
  • Substrate 13 of Table 1 eta-Borylation of Triisopropyl(4- isopropylphenoxy)silane:
  • the microreactor was capped with a Teflon pressure cap and placed into pre-heated aluminum block at 80 °C and stirred for 24 h. After completion (judged by GC-MS), CyH was removed under reduced pressure and chromatographic separation with neutral silica gel (2% EtOAc in hexane as eluent) gave 150.5 mg (72%) of the meto-borylated product as a colourless gummy liquid.
  • Substrate 19 of Table 1 eta-Borylation of (4- bromophenoxy)triisopropylsilane: In an argon-filled glove box, a 5.0 mL Wheaton microreactor was charged with [Ir(cod)OMe]2 (4.97 mg, 1.5 mol%), Ihpi (127.0 mg, 1.0 equiv.), ligand L2 (3.4 mg, 3.0 mol%), HBpin (3.2 mg, 5.0 mol%) and dry cyclohexane (1.0 mL) were added sequentially. The reaction mixture was stirred for 2 minutes at room temperature and then (4-bromophenoxy)triisopropylsilane (0.5 mmol, 164 mg) was added.
  • the microreactor was capped with a Teflon pressure cap and placed into pre-heated aluminum block at 50 °C and stirred for 24 h. After completion (judged by GC-MS), CyH was removed under reduced pressure and chromatographic separation with neutral silica gel (2% EtOAc in hexane as eluent) gave 163.4 mg (72%) of the meto-borylated product as a colourless gummy liquid.
  • Substrate 21 of Table 1 eta-Borylation of triisopropyl((5, 6,7,8- tetrahydronaphthalen-2-yl)oxy)silane:
  • the microreactor was capped with a Teflon pressure cap and placed into pre-heated aluminum block at 80 °C and stirred for 24 h. After completion (judged by GC-MS), CyH was removed under reduced pressure and chromatographic separation with neutral silica gel (2% EtOAc in hexane as eluent) gave 139.7 mg (65%) of the meto-borylated product as a colorless gummy liquid.
  • a 5.0 mL Wheaton microreactor was charged with catalyst-1 (7.9 mg, 3.0 mol%) or catalyst-2 (7.8 mg, 3.0 mol%) or catalyst-3 (7.7mg, 3.0 mol%), B2pin2 (127.0 mg, 1.0 equiv.), and dry cyclohexane (1.0 mL) were added sequentially.
  • the reaction mixture was stirred for 2 minutes at room temperature and then substrate (0.5 mmol) was added.
  • the microreactor was capped with a Teflon pressure cap and placed into pre-heated aluminum block at 40 °C for 24 h.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)

Abstract

La présente invention concerne la méta-borylation du phénol protégé par TIPS avec un nouveau type de structure de ligand ayant une fraction pyridone dans le noyau bipyridine (PY- PYRI). Cette nouvelle structure de ligand est hautement réactive et présente une borylation méta-sélective de divers phénols protégés par TIPS substitués et une réaction de borylation non affectée par l'encombrement stérique des substituants. La présente invention fournit un accès pour fonctionnaliser les méta-positions du phénol protégé par TIPS avec la nouvelle structure de ligand pyridine-pyridone avec [Ir(cod)OMe]2 et B2pin2 en tant qu'agent de borylation dans un solvant cyclohexane.
PCT/IN2023/050608 2022-06-25 2023-06-23 Nouvel échafaudage de ligand (py-pyri) pour la méta borylation de dérivés de phénol Ceased WO2023248253A1 (fr)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IN202011035905A (fr) * 2020-08-20 2022-02-25

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IN202011035905A (fr) * 2020-08-20 2022-02-25

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
CHATURVEDI JAGRITI, HALDAR CHABUSH, BISHT RANJANA, PANDEY GAJANAN, CHATTOPADHYAY BUDDHADEB: "Meta Selective C–H Borylation of Sterically Biased and Unbiased Substrates Directed by Electrostatic Interaction", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, vol. 143, no. 20, 26 May 2021 (2021-05-26), pages 7604 - 7611, XP093122219, ISSN: 0002-7863, DOI: 10.1021/jacs.1c01770 *
SALAMANCA VANESA, TOLEDO ALBERTO, ALBÉNIZ ANA C.: "[2,2′-Bipyridin]-6(1 H )-one, a Truly Cooperating Ligand in the Palladium-Mediated C–H Activation Step: Experimental Evidence in the Direct C-3 Arylation of Pyridine", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, vol. 140, no. 51, 26 December 2018 (2018-12-26), pages 17851 - 17856, XP093122221, ISSN: 0002-7863, DOI: 10.1021/jacs.8b10680 *
TATSUO ISHIYAMA, YUSUKE NOBUTA, JOHN F. HARTWIG, NORIO MIYAURA: "Room temperature borylation of arenes and heteroarenes using stoichiometric amounts of pinacolborane catalyzed by iridium complexes in an inert solventElectronic supplementary information (ESI) available: experimental procedures and spectral analyses of products. See http://www.rsc.org/suppdata/cc/b", CHEMICAL COMMUNICATIONS, ROYAL SOCIETY OF CHEMISTRY, UK, no. 23, 1 January 2003 (2003-01-01), UK , pages 2924, XP055342856, ISSN: 1359-7345, DOI: 10.1039/b311103b *
TROUVÉ JONATHAN, ZARDI PAOLO, AL‐SHEHIMY SHAYMAA, ROISNEL THIERRY, GRAMAGE‐DORIA RAFAEL: "Enzyme‐like Supramolecular Iridium Catalysis Enabling C−H Bond Borylation of Pyridines with meta ‐Selectivity", ANGEWANDTE CHEMIE INTERNATIONAL EDITION, VERLAG CHEMIE, HOBOKEN, USA, vol. 60, no. 33, 9 August 2021 (2021-08-09), Hoboken, USA, pages 18006 - 18013, XP093122218, ISSN: 1433-7851, DOI: 10.1002/anie.202101997 *
Y. KUNINOBU ET AL.: "A meta-selective C-H borylation directed by a secondary interaction between ligand and substrate", NATURE CHEMISTRY, vol. 7, no. 9, 17 August 2015 (2015-08-17), pages 712 - 717, XP055381705, DOI: 10.1038/nchem.2322 *

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