WO2015063543A1 - Hydridopalladium(ii) halides as preformed catalysts for suzuki-miyaura cross-coupling reactions - Google Patents
Hydridopalladium(ii) halides as preformed catalysts for suzuki-miyaura cross-coupling reactions Download PDFInfo
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- WO2015063543A1 WO2015063543A1 PCT/IB2013/059779 IB2013059779W WO2015063543A1 WO 2015063543 A1 WO2015063543 A1 WO 2015063543A1 IB 2013059779 W IB2013059779 W IB 2013059779W WO 2015063543 A1 WO2015063543 A1 WO 2015063543A1
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- Prior art keywords
- terf
- halides
- phosphine
- suzuki
- hydridopalladium
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 150000004820 halides Chemical class 0.000 title claims abstract description 26
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 title abstract description 28
- 238000006243 chemical reaction Methods 0.000 title abstract description 20
- -1 biaryl compounds Chemical class 0.000 claims abstract description 16
- 239000003446 ligand Substances 0.000 claims abstract description 15
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 23
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 11
- 125000005418 aryl aryl group Chemical group 0.000 claims description 7
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- 125000005621 boronate group Chemical class 0.000 claims description 5
- 238000006880 cross-coupling reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 150000003003 phosphines Chemical class 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- ANIAFEJRWQDKDV-UHFFFAOYSA-N bis(1-adamantyl)-benzylphosphane Chemical compound C1C(C2)CC(C3)CC2CC13P(C12CC3CC(CC(C3)C1)C2)CC1=CC=CC=C1 ANIAFEJRWQDKDV-UHFFFAOYSA-N 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 150000007529 inorganic bases Chemical group 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- 235000010290 biphenyl Nutrition 0.000 claims 2
- 239000004305 biphenyl Substances 0.000 claims 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims 1
- ICKDTPDWPKXRKM-UHFFFAOYSA-N OBO.OC1=CC=CC=C1O Chemical class OBO.OC1=CC=CC=C1O ICKDTPDWPKXRKM-UHFFFAOYSA-N 0.000 claims 1
- 150000004703 alkoxides Chemical class 0.000 claims 1
- 239000000010 aprotic solvent Substances 0.000 claims 1
- HTJWUNNIRKDDIV-UHFFFAOYSA-N bis(1-adamantyl)-butylphosphane Chemical compound C1C(C2)CC(C3)CC2CC13P(CCCC)C1(C2)CC(C3)CC2CC3C1 HTJWUNNIRKDDIV-UHFFFAOYSA-N 0.000 claims 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical class FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims 1
- LCSNDSFWVKMJCT-UHFFFAOYSA-N dicyclohexyl-(2-phenylphenyl)phosphane Chemical group C1CCCCC1P(C=1C(=CC=CC=1)C=1C=CC=CC=1)C1CCCCC1 LCSNDSFWVKMJCT-UHFFFAOYSA-N 0.000 claims 1
- ZRVANNJGPCSNAH-UHFFFAOYSA-N dicyclohexyl-[1-(2,4,6-trimethylphenyl)imidazol-2-yl]phosphane Chemical compound CC1=CC(C)=CC(C)=C1N1C(P(C2CCCCC2)C2CCCCC2)=NC=C1 ZRVANNJGPCSNAH-UHFFFAOYSA-N 0.000 claims 1
- JUZAKZRALSJLOV-UHFFFAOYSA-N dicyclohexyl-[1-(2-methoxyphenyl)pyrrol-2-yl]phosphane Chemical compound COC1=CC=CC=C1N1C(P(C2CCCCC2)C2CCCCC2)=CC=C1 JUZAKZRALSJLOV-UHFFFAOYSA-N 0.000 claims 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- 239000001294 propane Substances 0.000 claims 1
- 239000003586 protic polar solvent Substances 0.000 claims 1
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical group COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 claims 1
- ZGNPLWZYVAFUNZ-UHFFFAOYSA-N tert-butylphosphane Chemical compound CC(C)(C)P ZGNPLWZYVAFUNZ-UHFFFAOYSA-N 0.000 claims 1
- 150000001502 aryl halides Chemical class 0.000 abstract 1
- 125000005620 boronic acid group Chemical class 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000725 suspension Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 235000019439 ethyl acetate Nutrition 0.000 description 6
- 125000002524 organometallic group Chemical group 0.000 description 5
- JGBZTJWQMWZVNX-UHFFFAOYSA-N palladium;tricyclohexylphosphane Chemical compound [Pd].C1CCCCC1P(C1CCCCC1)C1CCCCC1.C1CCCCC1P(C1CCCCC1)C1CCCCC1 JGBZTJWQMWZVNX-UHFFFAOYSA-N 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 229910002666 PdCl2 Inorganic materials 0.000 description 3
- 150000001500 aryl chlorides Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- ABMYEXAYWZJVOV-UHFFFAOYSA-N pyridin-3-ylboronic acid Chemical compound OB(O)C1=CC=CN=C1 ABMYEXAYWZJVOV-UHFFFAOYSA-N 0.000 description 3
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 3
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 3
- RNHDAKUGFHSZEV-UHFFFAOYSA-N 1,4-dioxane;hydrate Chemical compound O.C1COCCO1 RNHDAKUGFHSZEV-UHFFFAOYSA-N 0.000 description 2
- WDZACGWEPQLKOM-UHFFFAOYSA-N 2-chloro-1,3,5-trimethylbenzene Chemical group CC1=CC(C)=C(Cl)C(C)=C1 WDZACGWEPQLKOM-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000009815 homocoupling reaction Methods 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QCSLIRFWJPOENV-UHFFFAOYSA-N (2-fluorophenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1F QCSLIRFWJPOENV-UHFFFAOYSA-N 0.000 description 1
- LKNANEBKEYKHMI-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2-methylphenyl)benzene Chemical group CC1=CC(C)=CC(C)=C1C1=CC=CC=C1C LKNANEBKEYKHMI-UHFFFAOYSA-N 0.000 description 1
- BHMMHIHPBQFYOA-UHFFFAOYSA-N 3-(2,4,6-trimethylphenyl)pyridine Chemical compound CC1=CC(C)=CC(C)=C1C1=CC=CN=C1 BHMMHIHPBQFYOA-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000012565 NMR experiment Methods 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001543 aryl boronic acids Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000007819 coupling partner Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000012694 precious metal precursor Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000006894 reductive elimination reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- MQYZHXLHUNLBQH-UHFFFAOYSA-N tert-butyl(dicyclohexyl)phosphane Chemical compound C1CCCCC1P(C(C)(C)C)C1CCCCC1 MQYZHXLHUNLBQH-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000010507 β-hydride elimination reaction Methods 0.000 description 1
Classifications
-
- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
- C07B37/04—Substitution
-
- 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
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
-
- 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
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
-
- 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
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
- B01J2231/4227—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group with Y= Cl
-
- 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
- B01J2531/824—Palladium
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/121—Metal hydrides
Definitions
- the present invention demonstrates the use of hydridopalladium(ll) halides 1 a-d in the Suzuki-Miyaura reaction between sterically hindered electron-rich aryl chlorides and ⁇ / ⁇ /70-substituted aryl boronic acids (Table 1 ).
- the efficiency of hydridopalladium(ll) halides 1 a-b as catalysts in the Suzuki-Miyaura cross-coupling reactions was compared to the corresponding Pd(ll) halides L 2 PdCl2 and L n Pd(0) complexes, which both contain the same ligands L.
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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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to application of well-defined air and moisture stable hydridopalladium(ll) halides LnPd(H)(X), where L is ligand and X is halide, as preformed catalysts in the Suzuki-Miyaura cross-coupling reactions between arylboron derivatives (boronic acids, pinacolylboronates) and aryl halides in the production of biaryl compounds.
Description
HYDRIDOPALLADIUM(II) HALIDES AS PREFORMED CATALYSTS FOR SUZUKI-MIYAURA CROSS-COUPLING REACTIONS
Field of the invention
The present invention relates to chemistry, and particularly to the use of well-defined hydridopalladium(ll) halides of a general formula LnPd(H)(X) as catalysts for Suzuki-Miyaura cross-coupling reaction. This invention is particularly relevant for, but not limited to, the industrial-scale Suzuki-Miyaura cross-coupling reaction.
Background of the invention
Palladium-catalyzed Suzuki-Miyaura cross-coupling reaction has found broad application in chemical and pharmaceutical industry as an efficient tool for the construction of new C-C bonds. Commonly used catalysts for the cross-coupling are preformed LnPd(0) complexes containing triaryl- and trialkylphosphines as ligands. Among them, triarylphosphines (L=PPh3 or P(o- tolyl)3) have been traditionally used owing to relatively low cost and sufficient stability. However, triarylphosphines are efficient as ligands only for the cross- coupling of relatively active halides such as iodides and bromides. The use of challenging substrates such as sterically hindered coupling partners as well as less reactive but more widely available chlorides often requires the use of electron-rich trialkylphosphines as ligands for Pd(0) (Fu, G. C. Acc. Chem. Res. 2008, 41, 1555).
The preformed catalytically active L2Pd(0) complexes possessing electron-rich trialkylphosphines typically are highly air sensitive. Dioxygen easily adds to Pd(0) center, forming palladium (II) peroxo species, which catalyzes homocoupling side-reactions (Adamo, C. et al J. Am. Chem. Soc. 2008, 128, 6829). Because handling of L2Pd(0) complexes requires especial precautions, they are relatively rarely utilized as catalysts in large-scale industrial cross-coupling processes. To overcome the catalyst's instability issue, the L2Pd(0) complexes are generated in situ from triaryl- and trialkylphosphines and a suitable Pd source such as Pd(OAc)2 (Amatore, C. et
al Organometallics 1995, 14, 1818) or PdCI2, Pd(dba)2 (Amatore, C. et al Organometallics 1993, 12, 3168), Pd2(dba)3 and Pd(n3-1 -PhC3H4)(n5-C5H5) (Fraser, A. W. et al Organometallics 2012, 31, 2470). This approach, however, is compromised by poor stability of trialkylphosphines, which typically are highly air-sensitive and often pyrophoric. Besides, in situ generation of the L2Pd(0) catalyst from Pd(dba)x (x=1 .5 or 2) and phosphines can bring about reproducibility problems associated with difficulty in controlling the proper ratio of phosphine ligands to Pd. Furthermore, it has also been demonstrated that the dba ligand remains ligated to L2Pd(0) complex forming a tri -coord in ate L2Pd(dba) species (Fairlamb, I. J. S. Org. Biomol. Chem. 2008, 6, 3645) which are less efficient as catalysts in the cross-coupling reaction (Amatore, C. et al Organometallics 1993, 12, 3168). Finally, various batches of commercially available Pd2(dba)3 may contain different amounts of Pd nanoparticles (up to 40%) (Zalesskiy, S. S.; Ananikov, V. P. Organometallics 2012, 31, 2302) which renders difficult a reproducibility of the Suzuki-Miyaura cross-coupling.
Catalytically active Pd(0) species for the Suzuki-Miyaura cross-coupling reactions can also be generated in situ from Pd(ll) halides L2PdCI2, where L=Cy3P (Colacot, T. J.; Shea, H. A. Org. Lett. 2004, 6, 3731 . Simmons, E. M.; Hartwig, J. F. J. Am. Chem. Soc. 2010, 132, 17092), 4-Me2N-C6H4P(f-Bu)2 (Guram, A. S. et al Org. Lett. 2006, 8, 1787. He, A.; Falck, J. R. J. Am. Chem. Soc. 2010, 132, 2524) and (CioH5N)P(C6Hii)2 (Bolliger, J. L; Freeh, C. M. Chem.-Eur. J. 2010, 16, 4075), as well as from (PPh3)2Pd(A/-Succ)Br (Burns, M. J. Et al Org. Lett. 2007, 9, 5397). These well-defined Pd(ll) complexes feature pre-installed phosphine ligands in a 2:1 phosphine to Pd ratio. They are moisture and air-stable and therefore can be conveniently handled. However, in situ transformation of Pd(ll) halides L2PdCI2 to catalytically active L2Pd(0) species may involve generation of homocoupling side-product, which complicates isolation of the desired product, especially if relatively high catalyst loading is employed (Butters, M. et al. Angew. Chem. Int.Ed. 2010, 49, 5156).
Thus, the development of air and moisture stable, well-defined palladium catalyst precursors for the Suzuki-Miyaura cross-coupling in industrial scale is highly desirable.
Description of the invention
In the first aspect, the present invention features the use of well-defined hydridopalladiunn(ll) halides of a general formula LnPd(H)(X) 1 as catalysts for Suzuki-Miyaura cross-coupling reaction. Considerable air- and moisture stability of the hydridopalladium(ll) halides 1 makes them superior the known LnPd(0) complexes. This invention is particularly relevant for, but not limited to, the industrial-scale Suzuki-Miyaura cross-coupling reaction.
In the presence of a suitable base, hydridopalladium(ll) halides
LnPd(H)(X) 1 undergo facile base-mediated reductive elimination of H-X to form L„Pd(0) species (Colacot, T. J.ef a/ Org. Lett. 2010, 12, 3332. Hills, I. D.; Fu, G. C. J. Am. Chem. Soc. 2004, 126, 13178. ). Because the Suzuki- Miyaura cross-coupling reaction requires the presence of stoichiometric amounts of base, hydridopalladium(ll) halides 1 are convenient precursors to catalytically active Pd(0) species (eq 1 ).
H \ / PR, 3 base
.Pd (R3P)2Pd (1 )
R3P X
1
Hydridopalladium(ll) halides LnPd(H)(X) 1 could be readily obtained from inexpensive precursors, preferably Pd(olefin)(X)2 in a β-hydride elimination reaction, in the presence of suitable phosphine ligand (eq 2) (Goel, A. B.; Goel, S. Inorg. Chim. Acta 1980, 45, L85-L86. Colacot, T. J.ef al Org. Lett. 2010, 12, 3332).
In another aspect, the present invention broadly relates to the use of well-defined hydridopalladium(ll) halides LnPd(H)(X) 1 as catalysts for Suzuki-
Miyaura cross-coupling reaction between aryl- and heteroaryl halides and aryl and heteroaryl boron derivatives.
Electron-rich bulky tricyclohexylphospine and tert- butyldicyclohexylphosphine are the most suitable phosphine ligands as they afford the best results in the Suzuki-Miyaura cross-coupling reaction. Other bulky phosphines such as, but not limited to, benzyl-di-1 -adamantylphosphine and (4-(/V,/V-dimethylamino)phenyl)di-terf-butyl phosphine, and mixtures or combinations thereof can be used.
Although in the most embodiments aryl- and heteroaryl chlorides are the preferred halogenated aryls for the Suzuki-Miyaura cross-coupling using the hydridopalladium(ll) halides 1 , aryl- and heteroaryl halides such as bromides and iodides can be used as well .
In the most embodiments aryl- and heteroaryl boronic acids are employed in the Suzuki-Miyaura cross-coupling, catalyzed by the hydridopalladium(ll) halides 1 . However, aryl- and heteroaryl pinacolyl boronates could also be used.
Any inorganic base compatible with the solvent are suitable for the
Suzuki-Miyaura cross-coupling, which is catalyzed by hydridopalladium(ll) halides 1 . The most preferred bases include, but are not limited to, CsF and K3PO4. Other carbonates, phosphates, acetates or fluorides such as CsOAc,
KOAc, NaOAc, K2CO3, Na2CO3, CS2CO3, KF and mixture or combinations thereof are suitable as base.
In one embodiment, the present invention demonstrates the use of hydridopalladium(ll) halides 1 a-d in the Suzuki-Miyaura reaction between sterically hindered electron-rich aryl chlorides and ο/ΐ/70-substituted aryl boronic acids (Table 1 ). The efficiency of hydridopalladium(ll) halides 1 a-b as catalysts in the Suzuki-Miyaura cross-coupling reactions was compared to the corresponding Pd(ll) halides L2PdCl2 and LnPd(0) complexes, which both contain the same ligands L. The general reaction conditions are: aryl chloride (0.3 mmol, 1 .0 equiv), aryl boronic acid (0.33 mmol, 1 .1 equiv.), CsF (0.9 mmol, 3.0 equiv.), hydridopalladium(ll) halide 1 a-d (0.0015 mmol, 5mol%), dioxane (3 ml_), 100 °C.
Table 1 . Suzuki-Miyaura cross-coupling with different catalysts 1 a-d, 2a-b, 3a-b.
Pd catalyst 1-3
(5 mol%)
Ar1— CI + Ar2— B(OH),
'2 — CsF—— *" Ar1 Ar2
(3 eq)
dioxane (100 °C)
1 a (Cy3P)2Pd(H)CI 2a: (Cy3P)2Pd
1 b (Cy2Pf-Bu)2Pd(H)CI 2b: (Cy2Pf-Bu)2Pd
1 c: (Cy3P)2Pd(H)Br 3a: (Cy3P)2PdCI2
1 d (Cy2Pf-Bu)2Pd(H)Br 3b: (Cy2Pf-Bu)2PdCI2
In general, hydridopalladium(ll) halide catalysts 1 a-d and the corresponding LnPd(0) complexes 2a, b provided comparable yields of the Suzuki-Miyaura cross-coupling products. Importantly, different Pd(ll) complex L2PdCl2 3a was inferior as catalyst in terms of yields. Furthermore, in one example (entry 5, Table 1 ) catalyst 3a was totally inefficient.
In another embodiment, the present invention includes the use of hydridopalladium(ll) halide 1 a as catalyst for the Suzuki-Miyaura reaction
between sterically hindered electron-rich aryl chlorides and ο/ΐ/70-substituted aryl pinacolyl boronates.
1 a: (Cy3P)2Pd(H)CI Yield using catalyst 1 a: 85% 2a: (Cy3P)2Pd Yield using catalyst 2a: 74%
In another embodiment, the present invention includes the use of hydridopalladium(ll) halide 1 a as catalyst for the Suzuki-Miyaura reaction between sterically hindered electron-rich aryl and heteroaryl chlorides and pyridine-3-boronic acid. The efficiency of hydridopalladium(ll) halides 1 a-b as catalysts in the Suzuki-Miyaura cross-coupling reactions was compared to the corresponding (CysP^PdC^ complex 3a and (Cy3P)2Pd complex 2a, which both contain the same ligands L. The general reaction conditions are: aryl or heteroaryl chloride (0.3 mmol, 1.0 equiv), pyridyl-3-boronic acid (0.33 mmol, 1.1 equiv), K3PO4 (0.51 mmol, 1.7 equiv), Pd catalyst (0.0015 mmol, 5 mol%), 2:1 dioxane-water (1.5 ml_), 100 °C.
Table 2.
Pd catalyst
dioxane-water 2:1
100 °C
6 70 92 38
H
4 CI
1
6 91 94 61
H
In general, hydridopalladiunn(ll) halide 1 a and the corresponding (Cy3P)2Pd complex 2a provided comparable yields of the Suzuki-Miyaura cross-coupling products, whereas Pd(ll) complex (Cy3P)2PdCl2 3a was inferior as catalyst in terms of yields.
The invention is illustrated with the following non-limiting examples. All solvents and reagents were purchased from commercial sources (e.g. Alfa Aesar, Sigma Aldrich) and used as received. All ligands or precious metal precursors were obtained from Strem Chemicals. All reactions were performed under inert atmosphere. All air and moisture sensitive reagents were handled in the glove box. Palladium hydrides L2Pd(H)(X) were synthesized according to literature procedure (Colacot, T. J.ef al Org. Lett. 2010, 12, 3332) from corresponding Pd(COD)X2 complexes and phosphine ligands L. Solvents for the Suzuki-Miyaura reaction was degassed by freeze- thaw method prior to use.
1 H, 13C, and 31 P-NMR spectra were recorded on a Varian Mercury-400 spectrometer. All 1 H NMR experiments are reported in δ units, parts per million (ppm) downfield from tetramethylsilane (internal standard) and were measured relative to the signals for residual chloroform (7.26 ppm). The yields in Tables 1 -2 refer to isolated yields (average of two runs) of compounds estimated to be >95% pure as determined by 1 H NMR. Conversion of starting compound is monitored by GC analysis that were performed on Agilent 7890A with MS detector Agilent 5975C, column HP-5MS, 30m x 0,25mm x 0,25μηη. Temperature gradient: 50°C (1 min), 50-80°C (5°C/min), 80-250°C (15°C/min), 250°C (10 min).
Example 1 . Preparation of Pd(PCy3)2(H)CI (1 a)
A suspension of Pd(COD)Cl2 (100 mg, 0.35 mmol) in anhydrous toluene (1 mL) was cooled to 0 °C. A solution of NaOMe (prepared by
dissolving NaOH (17 mg, 0.42 mmol) in 0.3 mL of anhydrous MeOH) was added via cannula, and stirring at 0 °C was continued for 20 min. The resulting pale-yellow suspension was added to a cold (0 °C) solution of PCy3 (196.3 mg, 0.70 mmol) in anhydrous toluene (2.2 mL). After stirring at 0 °C for 2.5 h, a colorless suspension was formed, which dissolved upon addition of cold (0 °C) MeOH (15 mL). The clear solution was kept in freezer (-18 °C) for 72 hours whereupon precipitate was formed . Filtration and drying in vacuo afforded 1 a as colorless crystals, 108 mg (44% yield).
1 H NMR (400 MHz, CDCI3) δ 2.08 (tt, 6H, J=12.2, 2.8 Hz), 2.02-1 .94 (m, 12H), 1 .85-1 .63 (m, 18H), 1 .54-1 .43 (m, 1 2H), 1 .35-1 .13 (m, 18H), -15.10 (t, 1 H, J=6.4 Hz).
13C-NMR (100 MHz, CDCI3) δ 34.1 (t, JC_P=9.9 Hz), 30.4, 27.4 (t, Jc- P=5.4 Hz).
31 P-NMR (400 MHz, CDCI3) δ 40.64.
Anal . Calcd for C36H67CI P2Pd: C 61 .44, H, 9.60. Found C 61 .59, H 9.88
Example 2. Preparation of Pd(PCy3)2(H)Br (1 b)
A suspension of Pd(COD)Br2 (200 mg, 0.53 mmol) in anhydrous toluene (1 mL) was cooled to 0 °C. A solution of NaOMe (prepared by dissolving NaOH (25.6 mg, 0.64 mmol) in 0.5 mL of anhydrous MeOH) was added via cannula, and stirring at 0 °C was continued for 20 min. The resulting pale-yellow suspension was added to a cold (0 °C) solution of PCy3 (329.5 mg, 1 .18 mmol) in anhydrous toluene (2.5 mL). After stirring at 0 °C for 2.5 h, a colorless suspension was formed, which dissolved upon addition of cold (0 °C) MeOH (25 mL). The clear solution was kept in freezer (-18 °C) for 24 hours whereupon precipitate was formed . Filtration and drying in vacuo afforded 1 b as colorless crystals, 346 mg (87% yield).
1 H NMR (400 MHz, CDCI3) δ 2.08 (tt, 6H, J=12.2, 2.8 Hz), 2.02-1 .93 (m, 12H), 1 .82-1 .65 (m, 18H), 1 .55-1 .40 (m, 1 2H), 1 .34-1 .1 1 (m, 18H), -14.0 (t, 1 H, J=6.4 Hz).
13C-NMR (100 MHz, CDCI3) δ 34.7 (t, Jc-P=10.2 Hz), 30.4, 27.4 (t,
31 P-NMR (400 MHz, CDCI3) δ 40.56.
Anal . Calcd for C36H67BrP2Pd: C 57.79, H, 9.03. Found C 58.10, H 8.86
Example 3. Preparation of Pd(PCy2t-Bu)2(H)CI (1 c)
A suspension of Pd(COD)Cl2 (150 mg, 0.53 mmol) in anhydrous toluene (2 mL) was cooled to 0 °C. A solution of NaOMe (prepared by dissolving NaOH (25 mg, 0.64 mmol) in 1 .0 mL of anhydrous MeOH) was added via cannula, and stirring at 0 °C was continued for 20 min. The resulting pale-yellow suspension was added to a cold (0 °C) solution of PCy2f-Bu (295 mg, 1 .16 mmol) in anhydrous toluene (3 mL). After stirring at 0 °C for 2.5 h, a colorless suspension was formed, which dissolved upon addition of cold (0 °C) MeOH (20 mL). The clear solution was kept in freezer (- 18 °C) whereupon precipitate was formed. Filtration and drying in vacuo afforded 1 c as colorless crystals, 60 mg (9% yield).
1 H-NMR (400 MHz, CDCI3) δ 3.47 (s, 1 H), 2.25-2.15 (m, 8H), 2.02- 1 .96 (m, 4H), 1 .84-1 .47 (m, 20H), 1 .42-1 .10 (m, 29H), -15.43 (t, 1 H, J=5.8 Hz).
13C-NMR (100 MHz, CDCI3) δ 34.7 (t, Jc-P=8.2 Hz), 33.6 (t, Jc-P=9.0 Hz), 31 .7, 30.8, 29.3, 27.6 (t, Jc-P=6.0 Hz), 27.3 (t, Jc-P=4.5 Hz), 26.5.
31 P-NMR (400 MHz, C6D6) δ 55.50. Example 4. Preparation of Pd(PCy2t-Bu)2(H)Br (1 d)
A suspension of Pd(COD)Br2 (100 mg, 0.27 mmol) in anhydrous toluene (1 mL) was cooled to 0 °C. A solution of NaOMe (prepared by dissolving NaOH (13.0 mg, 0.32 mmol) in 0.5 mL of anhydrous MeOH) was added via cannula, and stirring at 0 °C was continued for 20 min. The resulting pale-yellow suspension was added to a cold (0 °C) solution of PCy2f-Bu (149 mg, 0.59 mmol) in anhydrous toluene (1 .1 mL). After stirring at 0 °C for 2.5 h, a colorless suspension was formed, which dissolved upon addition of cold (0 °C) MeOH (10 mL). The clear solution was kept in freezer (-18 °C) for 15 min whereupon precipitate was formed. Filtration and drying in vacuo afforded 1 d as colorless crystals, 160 mg (86% yield).
1 H-NMR (400 MHz, CDCI3) δ 3.47 (s, 1 H), 2.28-2.16 (m, 8H), 2.03- 1 .95 (m, 4H), 1 .83-1 .48 (m, 20H), 1 .41 -1 .13 (m, 29H), -14.24 (t, 1 H, J=7.4).
13C-NMR (1 00 MHz, CDCI3) δ 34.7 (t, JC-P=8.3 Hz), 33.5 (t, Jc-P= 9.2 Hz), 31 .7 (t, JC-P=2.3 Hz), 30.7 (t, JC-P=2.9 Hz), 29.1 , 27.3 (t, JC-P=6.3 Hz), 27.1 (t, JC-P=4.8 Hz), 26.3.
31P-NMR (400 MHz, CDCI3) δ 53.71 .
Anal. Calcd for C32H63BrP2Pd: C 55.21 , H, 9.12. Found C 55.01 , H 9.43
Example 5. (PCy3)2Pd(H)(CI) as catalyst in the synthesis of 2,4,6,2'- tetramethyl-biphenyl in Suzuki-Miyaura reaction.
An oven dried reaction flask with screw cap containing a magnetic stir bar was placed in a„glove box" and charged with 2-fluorophenylboronic acid (46 mg, 0.33 mmol, 1 .1 eq), (PCy3)2Pd(H)(CI) catalyst (10.5 mg, 0.015 mmol, 0.05 eq), and CsF (137 mg, 0.9 mmol, 3eq; CsF is highly moisture sensitive). Flask was closed with septa, removed from„glove box" and dry degassed 1 ,4-dioxane (3 ml_) and 2-chloromesitylene (44 μΙ_, 0.3 mmol, 1 eq) were added by syringe. Septum was replaced with screw cap and reaction mixture was heated in oil bath at 100 °C for 16 h. The mixture was then diluted with EtOAc (5 ml_) and filtered trough a Celite pad (20x20mm), which was washed with EtOAc (3x5ml). Filtrate was dried over Na2SO4 and filtered through a plug of silica (20x20mm). The silica plug was washed with EtOAc (3x5ml), evaporated and dried in vacuo, yielding the product as colorless oil: run 1 :58 mg (90%), run 2: 59 mg (92%).
1H NMR (400 MHz, CDCIs) 5 7.37 - 7.30 (m, 1 H), 7.22 - 7.10 (m, 3H),
6.96 (s, 2H), 2.34 (s, 3H), 2.03 (s, 6H).
Example 6. (PCy3)2Pd(H)(CI) as catalyst in the synthesis of 3-(2,4,6-trimethyl- phenyl)-pyridine in Suzuki-Miyaura reaction.
100°C, 6h
3-Pyridineboronic acid (43 mg, 0.35 mnnol, 1 .1 eq) and
(PCy3)2Pd(H)(CI) (1 1 .3 mg, 0.016 mmol, 0.05 eq) were added to a reaction flask equipped with a stir bar. The flask was closed with septa and flushed with argon. 1 ,4-Dioxane (2 mL), 2-chloromesitylene (48 μί, 0.32 mmol, 1 eq) and aqueous K3PO4 (0.54M, 1 mL, 1 .7 eq) were added by syringe. Septum was replaced by a screw cap and the flask was heated in an oil bath at 100 °C for 6 h. The mixture was then diluted with EtOAc (5 mL) and filtered trough a Celite pad (20x20mm). The Celite pad was washed with EtOAc (3x5mL). Filtrate was dried over Na2SO4 and filtered through a plug of silica (20x20mm). The silica plug was washed with EtOAc (3x5mL), concentrated and dried in vacuo. The residue is colorless oil which crystallized upon standing: run 1 :57 mg (91 %), run 2: 58 mg (92%), run 3:59 mg (94 %).
H NMR (400 MHz, CDCI3) δ 8.60 (dd, J = 4.8, 1 .7 Hz, 1 H), 8.44 - 8.43
(m, 1 H), 7.50 (dt, J = 7.7, 1 .9 Hz, 1 H), 7.36 (dd, J = 7.7, 4.9 Hz, 1 H), 6.97 (s 2H), 2.34 (s, 3H), 2.01 (s, 6H).
Claims
1 . Use of hydridopalladium(ll) halides of general formula LnPd(H)Hal as catalysts for the C-C bond forming cross-coupling reaction between optionally substituted aryl- and heteroaryl boron derivatives and optionally substituted aryl- and heteroaryl halides in the presence of a base and a solvent, wherein: Hal is CI, Br or I,
L is a phosphine ligand,
n is 1 , when phosphine L is a bidentate phosphine, or
n is 2, when phosphine L is a monophosphine.
2. The use according to claim 1 , wherein ligand L is selected from the group of electron-rich phosphines, comprising phenyl-di-terf-butylphosphine, di-terf-butyl-neopentylphosphine, 1 ,2,3,4, 5-pentaphenyl-1 '-
(di-te/t-butylphosphino)ferrocene, triphenylphosphine, tricyclohexyl phosphine, tri(terf-butyl)phosphine, 1 -adamantyl-di-te/t-butylphosphine, benzyldi-1 - adamantylphosphine, butyldi-1 -adamantylphosphine, cyclohexyldi-terf- butylphosphine, 2-di-terf-butylphosphino-1 ,1 '-binaphtyl, 2-(di-terf- butylphosphino)biphenyl, 2-di-terf-butylphosphino-2'-(/V,/V- dimethylamino)biphenyl, 2-di-ie/t-butylphosphino-2',4',6'-th-/'-propyl-1 ,1 '- biphenyl, 2-(dicyclohexylphosphino) biphenyl, 2-(dicyclohexylphosphino)-2',6'- dimethoxy-1 ,1 '-biphenyl, 1 ,2-bis(di-terf-butylphosphinomethyl)benzene,
1 ,3-bis(di-te/t-butylphosphinomethyl)propane, 1 -(2-methoxyphenyl)-2-(di- cyclohexylphosphino)pyrrole, A/-phenyl-2-(dicyclohexylphosphino)indol, A/-phenyl-2-(di-cyclohexylphosphino)pyrrole and 1 -(2,4,6-trimethylphenyl)-2- (dicyclohexylphosphino)imidazole.
3. The use according to claim 1 , wherein aryl- and heteroaryl boron derivatives are selected from the group, comprising aryl- and heteroaryl boronic acids, pinacolyl boronates, catechol boronates, neopentylglycolato boronates, hexyleneglycolato boronates and trifluoroborates.
4. The use according to claim 1 , wherein said base is inorganic base, selected from the group comprising hydroxides, alkoxides, carbonates, phosphates or acetates and mixtures or combinations thereof.
5. The use according to claim 1 , wherein said solvent is selected from the group comprising protic solvents, aprotic solvents and combinations thereof.
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| CN114345370A (en) * | 2021-12-03 | 2022-04-15 | 陕西师范大学 | Method for reducing and cross-coupling aromatic olefin and halogenated hydrocarbon through photocatalysis |
| CN117986097A (en) * | 2024-01-15 | 2024-05-07 | 科莱博(江苏)科技股份有限公司 | Novel method for Suzuki coupling based on photocatalysis |
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| DE112013007542B4 (en) | 2021-05-12 |
| DE112013007542T5 (en) | 2016-07-21 |
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