WO2018106338A1 - Mono-ligated palladium catalysts, their synthesis and use in suzuki coupling - Google Patents
Mono-ligated palladium catalysts, their synthesis and use in suzuki coupling Download PDFInfo
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- WO2018106338A1 WO2018106338A1 PCT/US2017/055739 US2017055739W WO2018106338A1 WO 2018106338 A1 WO2018106338 A1 WO 2018106338A1 US 2017055739 W US2017055739 W US 2017055739W WO 2018106338 A1 WO2018106338 A1 WO 2018106338A1
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- Prior art keywords
- aryl
- alkyl
- formula
- composition according
- independently
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title abstract description 21
- 238000006069 Suzuki reaction reaction Methods 0.000 title abstract description 9
- 239000003054 catalyst Substances 0.000 title abstract description 9
- 229910052763 palladium Inorganic materials 0.000 title abstract description 9
- 230000015572 biosynthetic process Effects 0.000 title description 4
- 238000003786 synthesis reaction Methods 0.000 title description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 45
- 125000000217 alkyl group Chemical group 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 18
- -1 hexafluoroantimonate Chemical compound 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 150000001502 aryl halides Chemical class 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 150000001450 anions Chemical group 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- 125000005228 aryl sulfonate group Chemical group 0.000 claims description 5
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- WXHIJDCHNDBCNY-UHFFFAOYSA-N palladium dihydride Chemical compound [PdH2] WXHIJDCHNDBCNY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003880 polar aprotic solvent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- JCHVFUGWKCODDL-UHFFFAOYSA-N OBO.OC(=O)CN(C)CC(O)=O Chemical compound OBO.OC(=O)CN(C)CC(O)=O JCHVFUGWKCODDL-UHFFFAOYSA-N 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- PBIMIGNDTBRRPI-UHFFFAOYSA-N trifluoro borate Chemical compound FOB(OF)OF PBIMIGNDTBRRPI-UHFFFAOYSA-N 0.000 claims description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- PQISQOHUTDZDEU-UHFFFAOYSA-N F[P](F)(F)F Chemical compound F[P](F)(F)F PQISQOHUTDZDEU-UHFFFAOYSA-N 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 150000001350 alkyl halides Chemical class 0.000 claims 1
- 150000008051 alkyl sulfates Chemical class 0.000 claims 1
- 150000007942 carboxylates Chemical class 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- CTYRPMDGLDAWRQ-UHFFFAOYSA-N phenyl hydrogen sulfate Chemical compound OS(=O)(=O)OC1=CC=CC=C1 CTYRPMDGLDAWRQ-UHFFFAOYSA-N 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims 1
- 150000003003 phosphines Chemical class 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 abstract description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract 1
- 239000012041 precatalyst Substances 0.000 description 29
- 0 *C(N(*)c1c(*)c(*)c(*)c(*)c11)=**1(*I)I Chemical compound *C(N(*)c1c(*)c(*)c(*)c(*)c11)=**1(*I)I 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 125000002577 pseudohalo group Chemical group 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 150000004820 halides Chemical class 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 5
- FEJUGLKDZJDVFY-UHFFFAOYSA-N 9-borabicyclo[3.3.1]nonane Substances C1CCC2CCCC1B2 FEJUGLKDZJDVFY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical group [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-M fluorosulfonate Chemical compound [O-]S(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-M 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 150000007529 inorganic bases Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 2
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 2
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical group [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 150000001543 aryl boronic acids Chemical class 0.000 description 2
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- CXNIUSPIQKWYAI-UHFFFAOYSA-N xantphos Chemical compound C=12OC3=C(P(C=4C=CC=CC=4)C=4C=CC=CC=4)C=CC=C3C(C)(C)C2=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 CXNIUSPIQKWYAI-UHFFFAOYSA-N 0.000 description 2
- JGTNAGYHADQMCM-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-M 0.000 description 1
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 1
- AMKGKYQBASDDJB-UHFFFAOYSA-N 9$l^{2}-borabicyclo[3.3.1]nonane Chemical compound C1CCC2CCCC1[B]2 AMKGKYQBASDDJB-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910006095 SO2F Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005227 alkyl sulfonate group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 1
- 108010011222 cyclo(Arg-Pro) Proteins 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CZXGXYBOQYQXQD-UHFFFAOYSA-N methyl benzenesulfonate Chemical compound COS(=O)(=O)C1=CC=CC=C1 CZXGXYBOQYQXQD-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PANBFSGJYKYTNM-UHFFFAOYSA-N n'-phenylethanimidamide Chemical compound CC(N)=NC1=CC=CC=C1 PANBFSGJYKYTNM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- OOFGXDQWDNJDIS-UHFFFAOYSA-N oxathiolane Chemical compound C1COSC1 OOFGXDQWDNJDIS-UHFFFAOYSA-N 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229940066528 trichloroacetate Drugs 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- BQQJSZUDBXOSAG-UHFFFAOYSA-N tris(1-adamantyl)phosphane Chemical compound C1C(C2)CC(C3)CC2CC13P(C12CC3CC(CC(C3)C1)C2)C(C1)(C2)CC3CC2CC1C3 BQQJSZUDBXOSAG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
Definitions
- This invention relates generally to palladium catalysts and their method of manufacture.
- Transition metal e.g. palladium, nickel, or platinum
- aryl halide iodide, bromide, chloride
- aryl pseudohalides e. g. triflate, tosylate, mesylate, fluorosulfnate
- the activity of transition metal catalysts is greatly influenced by the structural features and the number of associated ligand to the metal. Mono-ligated Pd(0) catalysts, bearing one bulk and electron-rich ligand, havd been demonstrated to be effective.
- Mono-ligated Pd(0) catalyst have been generated in situ from mono-ligated palladium (II) precatalysts, such as biphenyl palladacycle precatalyst described in prior art WO2013/184198 Al by Buchwald, and mono-ligated allylpalladium (II) complex described in prior art WO2011161451 Al by Colacot. See also Chen et. al, Tri(l-adamantyl)phosphine: Expanding the Boundary of Electron-Releasing Character Available to Oroganophosphorous Compounds, J. Am. Chem. Soc. 2016, 138, 6392-6395.
- the present inventors have discovered mono-ligated palladium catalysts that are easy to synthesize and are effective in Suzuki coupling reactions.
- the invention is a composition comprising a compound of formula I
- L is a ligand
- Y is R 6 wherein R 6 is H, alkyl, aryl, or Y is OR7 where R7 is alkyl or aryl, or Y is NR8R9 wherein Rs, R9 are each independently, H, alkyl, aryl; and
- Ri -R4 are each independently, H, alkyl, aryl, alkoxy, aryloxy; Ri and R2, R2 and R3, or R3 and R 4 could form a cycle; and
- R5 and Rio are each independently, H, alkyl, aryl.
- a method comprising making the compound of formula I comprising reacting formula III in a solvent with a Pd(II) source and an acid (HX) at a temperature in the range of 20 °C to 100 °C and then reacting Formula II with two ligands, L, at 0 °C to 100 °C in a polar
- a method comprising reacting an aryl halide or pseudohalide with an organoboron compound in the presence of compound of Formula I.
- Ri - R 4 are selected from hydrogen, alkyl, and alkyloxy, where the alkyl and alkyloxy, preferably have from 1 to 20, more preferably 1 to 10, and most preferably 1-6 carbon atoms.
- the precatalyst has the formulae 1-7, 1-8, and 1-9
- Certain preferred precatalysts include:
- precatalysts include those selected from the group of
- the precatalyst of this invention can contain any of a variety of known ligands.
- the preferred ligands are trialkylphosphine, triarylphosphine, dialkylarylphosphine, alkyldiarylphosphine, bis(phosphine), phosphoramide, or N-heterocyclic carbene.
- the ligands may be selected from the group consisting of triphenylphosphine (PI13P), tri-t- butylphosphine(P(t-Bu)3), tricyclohexylphosphine (P(Cy)3) , tri(o-tolyl)phosphine( P(o- tol) 3 ), (+)-2,2'-Bis(diphenylphosphino)- 1 , 1 '-binaphthalene((+)-BINAP), 1,1'-
- Me is methyl
- i-Pr isopropyl
- Cy is cyclohexyl
- tBu is t-butyl
- Ad is adamantyl
- Xi is N or CH
- R is alkyl, cycloalkyl or aryl of 1-20, preferably 1-10, more preferably 1-6 carbon atoms.
- R x is alkyl (such as butyl, adamantyl (Ad), benzyl, aryl
- N-heterocyclic carbene selected from imidazoline-2-ylidenes of the formula
- the anion X may be any anion but is preferably selected from group consisting of halide, alkylcarboxylate, boron tetrafluoride, tetraarylborates (such as B(C6Hs)4 ⁇ , and (B[3,5-(CF3)2C6H3]4) " ), alkylsulfonate, haloalkylsulfonate, and arylsulfonate.
- the anion is a halide selected from fluoride, chloride, bromide or iodide.
- X is alkylcarboxylate, and the alkyl is substituted or unsubstituted alkyl of 1 to 12 carbon atoms. Suitable substituents include halides (fluoro, chloro) and alkoxyl, aryloxyl, cyano, nitro, carbonyl. X may be acetate. X may be a haloalkylcarboxylate such as triflouroacetate (TFA) or trichloroacetate.
- TFA triflouroacetate
- X is alkylsulfonate, cycloalkyl or arylsulfonate, and the alkyl is a substituted or unsubstituted alkyl of 1 to 4 carbon atoms and the aryl may be a substituted or unsubstitued aryl of preferably 6 to 12 carbon atoms.
- X may be methylsulfonate, ethylsulfonate, methylphenylsulfonate or p-toluenesulfonate (TsO ).
- Suitable substituents include halides and alkoxyl, aryloxyl,cyano, nitro, carbonyl.
- X may be fluoroalkylsulfonate, such as trifluoromethylsulfonate (TfO ), nonafluorobutane sulfonate (NfO-).
- the invention relates to a method of making any one of the aforementioned precatalysts, according to Scheme 1 from a palladacycle dimer of Formula
- THF tetrahydrofuran
- CH2CI2 methylene chloride
- Conditions for the reaction may be in the range of 0 °C to about 40 °C.
- the reaction should be allowed to run until substantially complete which may occur in the range of 30 minutes to 20 hours. It is preferable to perform the reactions under an inert atmosphere using a gas such as nitrogen or argon.
- the dimers of Formula II may be obtained from any known source or may be made accordi
- the substrate of Formula III is obtained from a commercial source or prepared by known methods; X, Ri - R5, Rio and Y are defined above.
- the Pd(II) source may be any known suitable source but is preferably palladium acetate (Pd(OAc)2).
- the solvent may be a non-polar or a polar aprotic solvent. Preferred solvents are toluene, methylene chloride, THF, or 1,4-dioxane.
- the reaction in scheme 2 takes place at 20 °C to about 100 °C. The reaction is typically complete after about 30 minutes to 20 hours.
- This invention also relates to the application of any one of the aforementioned precatalysts in Suzuki-Miyaura cross-coupling reactions of Scheme 3: precatalyst
- the precatalyst is any one of the aforementioned precatalysts
- Rn is aryl, heteroaryl, alkyl, or alkenyl
- Xi is I, Br, CI, or sulfonate (such as triflate, nonflate, tosylate, mesylate,
- Ri2 is aryl, alkenyl, or alkyl, preferably of from 1 to 20, more preferably 1 to 10, and most preferably 1-6 carbon atoms ;
- B"*. is a boron functional group, which is preferably selected from a group consisting of boronic acid, boronic ester (e.g. boronic acid binacol ester (BPin)), potasium trifluoroborate (-BF3K), N-methyliminodiacetic acid boronate (BMIDA), etc.
- boronic ester e.g. boronic acid binacol ester (BPin)
- BP3K potasium trifluoroborate
- BMIDA N-methyliminodiacetic acid boronate
- An embodiment of this invention provides a process which comprises mixing, in a liquid medium, i) at least one base; ii) at least one aryl halide or aryl pseudohalide (as defined below) in which all substituents are other than boron functionalized groups, wherein the aryl halide has, directly bonded to the aromatic ring(s), at least one halogen atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom, wherein aryl pseudohalide has, directly bonded to the aromatic ring(s), at least one pseudohalide group selected from sulfonates consisting of triflate (OTf), tosylate (OTs), nonflate, mesylate (OMs), and fluorosulfonate (SO2F); iii) at least one organoboron compound selected from arylboronic acid, arylboronic ester, aryltrifluoroborate, aryl-9
- the liquid medium for the processes in this invention can include any of a wide range of solvents, and mixtures of solvents are also usable.
- the types of solvents that can be used include hydrocarbons, ethers, amides, ketones, alcohols, nitriles (acetonitrile), dimethyl sulfoxide, and water. Polar solvents are preferred.
- Ethers that may be used include, for example, 1 ,4-dioxane, tetrahydrofuran, glyme, diglyme.
- a large variety of bases are suitable for the processes in this invention. Generally, these are inorganic bases. Alkali metal salts are a preferred group of inorganic bases.
- alkali metal salts include, but are not limited to, sodium acetate, sodium bicarbonate, sodium carbonate, sodium tert-butoxide, sodium hydroxide, potassium bicarbonate, potassium carbonate, potassium phosphate, potassium hydroxide, potassium tert-botoxide, cesium bicarbonate, and cesium carbonate.
- Alkali metal salts of carboxylic acid anions e.g., acetate
- Amines e.g. triethylamine, pyridine
- Choice(s) of base will vary with the particular system of aryl halide or pseudohalide and organoboron compound involved.
- the aryl halide or pseudohalide has at least one halogen atom directly bonded to the aromatic ring(s) selected from a chlorine atom, a bromine atom, and a iodine atom, or at least one pseudohalide group.
- the term "pseudohalide group” includes such groups as arylsulfonate (e.g., p-toluenesulfonate (tosylate)), alkylsulfonate (e.g., methanesulfonate, OMs; trifluoromethanesulfonate (triflate)), and fluorosulfonate.
- the aryl moiety for the aryl halide or pseudohalide can be homocyclic or heterocyclic.
- suitable homocyclic aryl moieties include, but are not limited to benzene, naphthalene, anthracene,
- Heterocyclic aryl moieties that can be used include, for example, furan, thiophene, oxathiolane, nitrogen-containing heterocycles, such as pyridine, indole, and isoxazole, and the like.
- the organoboron compond in this invention is selected from aryl organoboron compounds, alkenyl organoboron compounds, and alkyl organoboron compounds.
- Suitable aryl organoboron compounds include arylboronic acid, arylboronic ester, aryl-BMIDA, aryltrifluoroborate, the aryl moieties are homocyclic or heteroyclic.
- Corresponding alkenyl and alkyl boron compounds may also be used in this invention.
- Suitable reaction temperature ranges are from 0 - 200 °C, preferably 20 - 80 °C.
- An embodiment of this invention is the Suzuki coupling of aryl halide/pesudohalide and aryl boron compound to generate biaryl compounds, illustrated in Scheme 3a
- Ar, Ari are each, independently, aryl groups (homocyclic or heterocyclic).
- the other components and reaction conditions are as discussed above.
- the second embodiment of this invention is the Suzuki coupling of aryl
- Ar is aryl groups (homocyclic or heterocyclic)
- R13 is an alkyl group, which can be non-cyclic or cyclic.
- the other components and reaction conditions are as discussed above.
- the third embodiment of this invention is the Suzuki coupling of alkyl
- R14 and R15 are each, independently, alkyl groups or cycloalkyl groups.
- the other components and reaction conditions are as discussed above.
- N-phenylacetimidaamide (0.6709 g, 5.0 mmol)
- 1,4-dioxane 10 mL
- Pd(OAc)2 1.1225 g, 5.0 mmol
- para-toluenesulfonic acid monohydrate 0.9501 g
- the mixture was stirred at ambient temperature overnight (16 h), resulting in a dark solution.
- t-BuOMe (20 mL) was added and the mixture was stirred for 10 min, resulting in precipitation of a semi-solid. The solvents were decanted.
- Example 5 The Suzuki Coupling reactions of 4-bromotoluene or 4-chlorotoluene and phenylboronic Acid
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Abstract
The present invention is mono-ligated palladium catalysts that are easy to synthesize and are effective in Suzuki coupling reactions. Specifically these catalysts are characterized by an aromatic ring having a substituent with two nitrogen atoms one of which associates with the palladium atom.
Description
MONO-LIGATED PALLADIUM CATALYSTS, THEIR SYNTHESIS
AND USE IN SUZUKI COUPLING
FIELD OF THE INVENTION
[001] This invention relates generally to palladium catalysts and their method of manufacture.
INTRODUCTION
[002] Transition metal (e.g. palladium, nickel, or platinum) catalyzed reactions of aryl halide (iodide, bromide, chloride), and aryl pseudohalides (e. g. triflate, tosylate, mesylate, fluorosulfnate) with various substrates is a general method employed for the formation of C- C, C-N, C-0 bonds, which plays an important role in synthesis of fine chemicals, agricultural and pharmaceutical products, and advanced materials. The activity of transition metal catalysts is greatly influenced by the structural features and the number of associated ligand to the metal. Mono-ligated Pd(0) catalysts, bearing one bulk and electron-rich ligand, havd been demonstrated to be effective. Mono-ligated Pd(0) catalyst have been generated in situ from mono-ligated palladium (II) precatalysts, such as biphenyl palladacycle precatalyst described in prior art WO2013/184198 Al by Buchwald, and mono-ligated allylpalladium (II) complex described in prior art WO2011161451 Al by Colacot. See also Chen et. al, Tri(l-adamantyl)phosphine: Expanding the Boundary of Electron-Releasing Character Available to Oroganophosphorous Compounds, J. Am. Chem. Soc. 2016, 138, 6392-6395.
SUMMARY OF INVENTION
[003] The present inventors have discovered mono-ligated palladium catalysts that are easy to synthesize and are effective in Suzuki coupling reactions.
[004] Thus, according to one aspect, the invention is a composition comprising a compound of formula I
Formula I
wherein X is an anion,
L is a ligand,
Y is R6 wherein R6 is H, alkyl, aryl, or Y is OR7 where R7 is alkyl or aryl, or Y is NR8R9 wherein Rs, R9 are each independently, H, alkyl, aryl; and
Ri -R4 are each independently, H, alkyl, aryl, alkoxy, aryloxy; Ri and R2, R2 and R3, or R3 and R4 could form a cycle; and
R5 and Rio are each independently, H, alkyl, aryl.
[005] A method comprising making the compound of formula I comprising reacting formula III in a solvent with a Pd(II) source and an acid (HX) at a temperature in the range of 20 °C to 100 °C and then reacting Formula II with two ligands, L, at 0 °C to 100 °C in a polar
Formula III Formula II Formula I
[006] A method comprising reacting an aryl halide or pseudohalide with an organoboron compound in the presence of compound of Formula I.
DETAILED DESCRIPTION
[007] For the Precatalysts of Formula I, preferably Ri - R4 are selected from hydrogen, alkyl, and alkyloxy, where the alkyl and alkyloxy, preferably have from 1 to 20, more preferably 1 to 10, and most preferably 1-6 carbon atoms.
[008] In certain embodiments, the precatalyst has the formula 1-1 (An embodiment of Formula I, wherein Y = R6 , R6 is H, alkyl or aryl, preferably of 1 to 20, more preferably 1 to 10, and most preferably 1-6 carbon carbon atoms, and Ri - R5 and Rio are as defined above and X and L are as defined herein):
Formula 1-1
[009] In certain embodiments, the precatalyst has the formula 1-2 (An embodiment of Formula I, wherein Y = OR7 , R7 is alkyl or aryl, preferably of 1 to 20, more preferably 1 to 10, and most preferably 1-6 carbon carbon atoms, and Ri - R5 and Rio are as defined above and X and L are as defined herein):
Formula I-2
[0010] In certain embodiments, the precatalyst has the formula 1-3 (An embodiment of Formula I, wherein Y = NR8R9 , Rs , R9 are each independently, H, alkyl or aryland Ri - and Rio are as defined above and X and L are as defined herein):
Formula I-3
[0011] In certain embodiments, the precatalyst has the formula 1-4 (An embodiment of Formula I and 1-1, wherein Ri, R2, R4 are H and Y = R6, R6 is H, alkyl or aryl, and R3, R5, Rio are as defined above and X and L are as defined herein):
Formula 1-4
[0012] In certain embodiments, the precatalyst has the formula 1-5 (An embodiment of Formula I and 1-2, wherein Ri, R2, R4 are H and Y = OR7, R7 is alkyl or aryl, and R3, R5, Rio are as defined above and X and L are as defined herein):
Formula 1-5
[0013] In certain embodiments, the precatalyst has the formula 1-6 (An embodiment of Formula I and 1-3, wherein Ri, R2, R4 are H and Y = NR8R9, Rs R9 are each independently, H, alkyl or aryl, and R3, R5, Rio are as defined above and X and L are as defined herein):
Formula 1-6
[0014] In certain embodiments, the precatalyst has the formulae 1-7, 1-8, and 1-9
(Embodiments of Formula I and I-l and 1-4 where Ri, R2, R4 are H and R3 is as shown, Me = methyl, Y = R6, and R5, R6 and Rio are as defined above and X and L are as defined
Formula 1-7 Formula 1-8 Formula 1-9
[0015] In certain embodiments, the precatalyst has the formulae 1-10, I-l 1, and 1-12 (Embodiments of Formula 1, 1-2 and 1-5 where Ri, R2, R4 are H and R3 is as shown, Y = OR7, and R5, R7 and Rio are as defined above and X and L are as defined herein :
Formula 1-10 Formula 1-11 Formula 1-12
[0016] In certain embodiments, the precatalyst has the formulae 1-13, 1-14, and 1-15 (Embodiments of Formula 1, 1-3 and 1-6 where Ri, R2, R4 are H and R3 is as shown, Y = defined herein):
Formula 1-13 Formula 1-14 Formula 1-15
[0017] In certain embodiments, the precatalyst has Formulae 1-16, 1-17 or 1-18, 1-19, 1-20 or 1-21 (subspecies of Formulae 1-7, 1-8 and 1-9 where R5 and Rio are H, Y = Me, or Ph
Formula 1-19 Formula I-20 Formula 1-21
The Ligand and Anion
[0020] The precatalyst of this invention can contain any of a variety of known ligands. Among the preferred ligands are trialkylphosphine, triarylphosphine, dialkylarylphosphine, alkyldiarylphosphine, bis(phosphine), phosphoramide, or N-heterocyclic carbene.
The ligands may be selected from the group consisting of triphenylphosphine (PI13P), tri-t- butylphosphine(P(t-Bu)3), tricyclohexylphosphine (P(Cy)3) , tri(o-tolyl)phosphine( P(o- tol)3), (+)-2,2'-Bis(diphenylphosphino)- 1 , 1 '-binaphthalene((+)-BINAP), 1,1'-
XantPhos
-11-
where Me is methyl, i-Pr is isopropyl, Cy is cyclohexyl, tBu is t-butyl, Ad is adamantyl, Xi is N or CH, R is alkyl, cycloalkyl or aryl of 1-20, preferably 1-10, more preferably 1-6 carbon atoms.
Rx is alkyl (such as butyl, adamantyl (Ad), benzyl, aryl
N-heterocyclic carbene, selected from imidazoline-2-ylidenes of the formula
Ar— N N-Ar
or protonated salts thereof (which generate imidazoline-2-ylidenes in the presence of a base), wherein Ar is an aryl, R' and R", each are independently, hydrogen, halo, alkyl, or aryl. R' and R" are structures
Mes IPr
[0021] The anion X may be any anion but is preferably selected from group consisting of halide, alkylcarboxylate, boron tetrafluoride, tetraarylborates (such as B(C6Hs)4~, and (B[3,5-(CF3)2C6H3]4)"), alkylsulfonate, haloalkylsulfonate, and arylsulfonate. According to one preferred embodiment, the anion is a halide selected from fluoride, chloride, bromide or iodide. According to another preferred embodiment, X is alkylcarboxylate, and the alkyl is substituted or unsubstituted alkyl of 1 to 12 carbon atoms. Suitable substituents include halides (fluoro, chloro) and alkoxyl, aryloxyl, cyano, nitro, carbonyl. X may be acetate. X may be a haloalkylcarboxylate such as triflouroacetate (TFA) or trichloroacetate.
[0022] According to another embodiment X is alkylsulfonate, cycloalkyl or arylsulfonate, and the alkyl is a substituted or unsubstituted alkyl of 1 to 4 carbon atoms and the aryl may be a substituted or unsubstitued aryl of preferably 6 to 12 carbon atoms. X may be methylsulfonate, ethylsulfonate, methylphenylsulfonate or p-toluenesulfonate (TsO ). Suitable substituents include halides and alkoxyl, aryloxyl,cyano, nitro, carbonyl. X may be fluoroalkylsulfonate, such as trifluoromethylsulfonate (TfO ), nonafluorobutane sulfonate (NfO-).
Method of Making Precatalysts
[0023] In certain emodiments, the invention relates to a method of making any one of the aforementioned precatalysts, according to Scheme 1 from a palladacycle dimer of Formula
Formula II Formula I
Scheme 1
[0024] Preferably the above reaction is run in a polar aprotic solvent such as
tetrahydrofuran (THF) or methylene chloride (CH2CI2). Conditions for the reaction may be in the range of 0 °C to about 40 °C. The reaction should be allowed to run until substantially complete which may occur in the range of 30 minutes to 20 hours. It is preferable to perform the reactions under an inert atmosphere using a gas such as nitrogen or argon.
[0025] The dimers of Formula II may be obtained from any known source or may be made accordi
Formula III Formula II
Scheme 2 wherein the substrate of Formula III is obtained from a commercial source or prepared by known methods; X, Ri - R5, Rio and Y are defined above. The Pd(II) source may be any known suitable source but is preferably palladium acetate (Pd(OAc)2). The solvent may be a non-polar or a polar aprotic solvent. Preferred solvents are toluene, methylene chloride, THF, or 1,4-dioxane. The reaction in scheme 2 takes place at 20 °C to about 100 °C. The reaction is typically complete after about 30 minutes to 20 hours.
Methods/Application of the Invention Suzuki Coupling
[0026] This invention also relates to the application of any one of the aforementioned precatalysts in Suzuki-Miyaura cross-coupling reactions of Scheme 3:
precatalyst
R-i -|— X-i + R12— Βί - *~ Ri i- R-I 2 base
solvent
organoboron tepmerature
Scheme 3
wherein,
the precatalyst is any one of the aforementioned precatalysts;
Rn is aryl, heteroaryl, alkyl, or alkenyl
Xi is I, Br, CI, or sulfonate (such as triflate, nonflate, tosylate, mesylate,
fluorosulfonate);
Ri2 is aryl, alkenyl, or alkyl, preferably of from 1 to 20, more preferably 1 to 10, and most preferably 1-6 carbon atoms ;
B"*. is a boron functional group, which is preferably selected from a group consisting of boronic acid, boronic ester (e.g. boronic acid binacol ester (BPin)), potasium trifluoroborate (-BF3K), N-methyliminodiacetic acid boronate (BMIDA), etc.
[0027] An embodiment of this invention provides a process which comprises mixing, in a liquid medium, i) at least one base; ii) at least one aryl halide or aryl pseudohalide (as defined below) in which all substituents are other than boron functionalized groups, wherein the aryl halide has, directly bonded to the aromatic ring(s), at least one halogen atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom, wherein aryl pseudohalide has, directly bonded to the aromatic ring(s), at least one pseudohalide group selected from sulfonates consisting of triflate (OTf), tosylate (OTs), nonflate, mesylate (OMs), and fluorosulfonate (SO2F); iii) at least one organoboron compound selected from arylboronic acid, arylboronic ester, aryltrifluoroborate, aryl-9- BBN (9-BBN refers to 9-borabicyclo[3.3.1]nonane), aryl-BMIDA, alkylboronic acid, alkylboronic ester, alkyl-9-BBN in which all substituents are other than chlorine atoms, bromine atoms, iodine atoms, or pseudohalide groups; iv) at least one of the aforementioned precatalysts, or in situ generated one of the aforementioned precatalysts via mixing of any one of aforementioned dimers and any one of the aforementioned ligands.
[0028] The liquid medium for the processes in this invention can include any of a wide range of solvents, and mixtures of solvents are also usable. The types of solvents that can be used include hydrocarbons, ethers, amides, ketones, alcohols, nitriles (acetonitrile), dimethyl sulfoxide, and water. Polar solvents are preferred. Ethers that may be used include, for example, 1 ,4-dioxane, tetrahydrofuran, glyme, diglyme.
[0029] A large variety of bases are suitable for the processes in this invention. Generally, these are inorganic bases. Alkali metal salts are a preferred group of inorganic bases.
Examples of suitable alkali metal salts include, but are not limited to, sodium acetate, sodium bicarbonate, sodium carbonate, sodium tert-butoxide, sodium hydroxide, potassium bicarbonate, potassium carbonate, potassium phosphate, potassium hydroxide, potassium tert-botoxide, cesium bicarbonate, and cesium carbonate. Alkali metal salts of carboxylic acid anions (e.g., acetate) are also suitable for use as an inorganic base in this invention. Amines (e.g. triethylamine, pyridine) are also suitable for use as a base in this invention. Choice(s) of base will vary with the particular system of aryl halide or pseudohalide and organoboron compound involved.
[0030] The aryl halide or pseudohalide has at least one halogen atom directly bonded to the aromatic ring(s) selected from a chlorine atom, a bromine atom, and a iodine atom, or at least one pseudohalide group. The term "pseudohalide group" includes such groups as arylsulfonate (e.g., p-toluenesulfonate (tosylate)), alkylsulfonate (e.g., methanesulfonate, OMs; trifluoromethanesulfonate (triflate)), and fluorosulfonate. The aryl moiety for the aryl halide or pseudohalide can be homocyclic or heterocyclic. Examples of suitable homocyclic aryl moieties include, but are not limited to benzene, naphthalene, anthracene,
phenanthrene, pyrene, biphenyl, fluorine and indene. Heterocyclic aryl moieties that can be used include, for example, furan, thiophene, oxathiolane, nitrogen-containing heterocycles, such as pyridine, indole, and isoxazole, and the like.
[0031] The organoboron compond in this invention is selected from aryl organoboron compounds, alkenyl organoboron compounds, and alkyl organoboron compounds. Suitable aryl organoboron compounds include arylboronic acid, arylboronic ester, aryl-BMIDA, aryltrifluoroborate, the aryl moieties are homocyclic or heteroyclic. Corresponding alkenyl and alkyl boron compounds may also be used in this invention.
[0032] Suitable reaction temperature ranges are from 0 - 200 °C, preferably 20 - 80 °C.
[0033] An embodiment of this invention is the Suzuki coupling of aryl halide/pesudohalide and aryl boron compound to generate biaryl compounds, illustrated in Scheme 3a
Precatalyst
Ar— X An-B^ base
+ ^ solvent Ar ΑΓι
temaperature
Scheme 3 a
wherein, Ar, Ari are each, independently, aryl groups (homocyclic or heterocyclic). The other components and reaction conditions are as discussed above.
[0034] The second embodiment of this invention is the Suzuki coupling of aryl
halides/pseudohalides and alkyl boron compounds, illustrated in Scheme 3b
Precatalyst
Ar— X . Ri3-B ^ψ- - Ar-R13
+ ¾ solvent 13
temaperature
Scheme 3b
Wherein, Ar is aryl groups (homocyclic or heterocyclic), R13 is an alkyl group, which can be non-cyclic or cyclic. The other components and reaction conditions are as discussed above.
[0035] The third embodiment of this invention is the Suzuki coupling of alkyl
halides/pseudohalides and alkyl boron compounds, illustrated in Scheme 3c
Precatalyst
base
14 + 15 -4. s eonllvuef-nntt R14 R15
temaperature
Scheme 3c
wherein, R14 and R15 are each, independently, alkyl groups or cycloalkyl groups. The other components and reaction conditions are as discussed above.
Examples
Example 1. Preparation of Di^-tosyloxy-bis(2-acetimidamidophenyl-2C,N)
dipalladium(II) (1)
1
In a 20-mL vial was added N-phenylacetimidaamide (0.6709 g, 5.0 mmol), 1,4-dioxane (10 mL) and the mixture was stirred. After the N-phenylacetimidamide was dissolved, Pd(OAc)2 (1.1225 g, 5.0 mmol), para-toluenesulfonic acid monohydrate (0.9501 g) were added. The mixture was stirred at ambient temperature overnight (16 h), resulting in a dark solution. t-BuOMe (20 mL) was added and the mixture was stirred for 10 min, resulting in precipitation of a semi-solid. The solvents were decanted. Fresh t-BuOMe (20 mL) was added to triturate the residue. The resulting solids were filtered, rinsed with t-BuOMe (5
mL), hexane (10 mL), and dried in a vacuum oven to give the desired product (1), 2.06 g (84%). !H-NMR (400 HMz/DMSO-d6) δ 10.27 (s, 1H), 7.49 (d, J = 8.0 Hz, 2H), 7.35 (d, J = 7.8 Hz, 1H), 7.20 (br s. 1H), 7.12 (d, J = 8.0 Hz, 2H), 7.04 (t, J = 7.8 Hz, 1H), 6.88 (d, J = 7.8 Hz, 1H), 6.76 (t, J = 7.8 Hz, 1H), 2.29 (s, 3 H), 2.27 (s, 3H).
Example 2. Preparation of Di^-tosyloxy-bis(2-benzimidamidophenyl-2C,N)
dipalladium(II) (2).
2
This compound was similarly prepared according to the preparation of compound 1 above. !H-NMR (400 HMz/DMSO-d6) δ 10.63 (s, 1H), 7.55-7.75 (m, 6H), 7.50 (d, J = 7.8 Hz, 2H), 7.45 (m. 1H), 7.05-7.18 (m, 4H), 2H), 6.88 (t, J = 7.8 Hz, 1H), 6.76 (t, J = 7.8 Hz, 1H), 2.28 (s, 3H).
Example 3. Tosyloxy-(2-acetimidamidophenyl-2C,N) (tri-cyclohexylphosphine) palladium (Π) (3)
In a 10 mL flask was added the palladacycle dimer 1 (0.2053 g, 0.5 mmol of monomer), tricyclohexylphosphine (0.1402 g, 0.5 mmol) and degassed THF (3 mL). The mixture was stirred at ambient temperature under nitrogen atmosphere overnight (16 h).The resulting brown solution was concentrated to about 1 mL, then hexane (10 mL) was added. The mixture was stirred for 1 h before filtration. The solid was filtered, rinsed with hexane (10 mL), and dried to give a grey solid, 0.30 g (87%). 1H-NMR (400 HMz/CDCh) δ 8.68 (m, 1H), 7.84 (d, J = 8.0 Hz, 2H), 7.30 (m, 1 H), 7.18 (d, J = 8.0 Hz, 2H), 6.94 (t, J = 7.2 Hz, , 1H), 6.74 (t, J = 7.2 Hz, , 1H), 6.66 (d, J = 7.2 Hz, , 1H), 2.37 (s, 3H), 2.34 (s, 3H), 2.1-0.9 (m, 33H).
Example 4. Tosyloxy-(2-benzimidamidophenyl-2C,N) (tri-cyclohexylphosphine) palladium (Π) (4)
Compound 4 was prepared similarly to compound 3 from palladacycle 2in 62% yield. 1H- NMR (400 HMz/CDCh) δ 9.31 (br s, 1H), 7.88 (m, 4H), 7.5-7.30 (m, 5 H), 7.16 (d, J = 8.0 Hz, 2H), 6.94 (t, J = 7.2 Hz, , 1H), 6.80 (m, 2H, 2.35 (s, 3 H), 2.1-0.9 (m, 33H).
Example 5: The Suzuki Coupling reactions of 4-bromotoluene or 4-chlorotoluene and phenylboronic Acid
Entry XI Precatalyst yield3
1 Br 3 70%
2 Br 4 77%
3 CI 3 45%
4 CI 4 48%
5 CI Pd(OAc)2/Cy3P (1: 1) 34%
1 estimated by H-NMR
General procedure: A palladium precatalyst (3 mol%) and phenylboronic acid (140.0 mg, 1.1 mmol, 1.1 equiv.) were added to a 25 mL tube flask under nitrogen. Then, a solution of 4-halotoluene (1.0 mmol) and octadecanol (internal standard, 0.50 mmol, 0.50 equiv) in ethanol (5 mL, degassed) was added, followed by addition of a solution of cesium carbonate (Cs2C03, 717 mg, 2.2 mmol, 2.2 equiv.) in water (1 mL, degassed). The tube was then heated and stirred at 60 °C for 1 h. A sample of the reaction mixture (~ 0.05 mL) was taken and analyzed by H-NMR (in CD C13) to determine yields.
Claims
1. A composition comprising a compound of Formula I
Formula I
wherein X is an anion,
L is a ligand,
Y is R6 wherein R6 is H, alkyl, aryl, or Y is OR7 where R7 is alkyl or aryl, or Y is NR8R9 wherein Rs, R9 are each independently, H, alkyl, aryl; and
Ri -R4 are each independently, H, alkyl, aryl, alkoxy, aryloxy; Ri and R2, R2 and R3, or R3 and R4 could form a cycle; and
R5 and Rio are each independently, H, alkyl, aryl.
2. The composition according to claim 1 wherein Y is R6, R6 is H, alkyl, or aryl.
3. The composition according to any one of claims 1-2 wherein Y is methyl or phenyl
4. The composition according to claim 1 wherein Y is OR7, R7 is alkyl, or aryl.
5. The composition according to claim 1, wherein Y is NR8R9, Rs, R9 are each
independently, H, alkyl of 1 to 20 carbon atoms, or R7 and Rs combine to form a cyclic group.
6. The composition according to any one of claims 1-5 wherein R5 and Rio are H.
7. The composition according to any one of claims 1-6 wherein Ri, R2, R3, R4 are
independently, alkyl, alkoxyl, of 1 to 20 carbon atoms, or H, provided at least one of Ri, R2, R3, R4 is alkyl or alkoxyl.
8. The composition according to claim 7 wherein Ri, R2, and R4 are H and R3 is methyl or methoxy
9. The composition according to any one of claims 1-7 wherein Ri, R2, R3, and R4 are H.
10. The composition according to any one of claim 1-9 wherein L is selected from
trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, and N-heterocylic carbene
11. The composition of claim 10 wherein L is all the specific phosphines herein.
12. The composition according to any one of claims 1-11, wherein X is selected from the group consisting of boron tetrafluoride, tetraarylborates; hexafluoroantimonate,
phosphorus tetrafluoride, phosphorus hexafluoride, alkylsulfonate, haloalkylsulfonate, arylsulfonate, perchlorate, bis(alkylsulfonyl)amide, bis(fluoroalkylsulfonyl)amide, bis(arylsulfonyl)amide, (fluoroalkylsulfonyl)(fluoroalkylcarbonyl)amide, nitrate, nitrite, sulfate, hydrogensulfate, alkylsulfate, aryl sulfate, carbonate, carboxylate, phosphate, hydrogen phosphate, dihydrogen phosphate, phosphinate, and hypochlorite.
13. A process for making the compound of any one of claims 1-10 comprising the reaction of Formula III in a solvent with a Pd(II) source and an acid, HX, at a temperature in the range of 0 °C to 100 °C
Formula III Formula II
wherein X is an anion,
Y is R6 wherein R6 is H, alkyl, aryl, or Y is OR7 where R7 is alkyl or aryl, or Y is NR8R9 wherein Rs, R9 are each independently, H, alkyl, aryl; and
Ri -R4 are each independently, H, alkyl, aryl, alkoxy, aryloxy; Ri and R2, R2 and R3, or R3 and R4 could form a cycle; and
R5 andRio are each independently, H, alkyl, aryl.
and then reacting Formula II with ligand, L, at 0 0 to 40 °C in a polar aprotic solvent to form the compound of any one of claims 1-10
14. A process comprising reacting an aryl or alkyl halide or aryl or alkyl or sulfonate with an organoboron compound in an organic solvent/water system in the presence of base and a composition of any of claims 1-12.
15. The process of claim 13 wherein an aryl halide or aryl sulfonate is reacted with the organoboron compound which has the formula r B- , where B""*- is a boron functional group, selected from a group consisting of boronic acid, boronic ester, potasium trifluoroborate, and N-methyliminodiacetic acid boronate, and Rio is an aryl group.
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