GB1580461A - Transition metal complexes - Google Patents
Transition metal complexes Download PDFInfo
- Publication number
- GB1580461A GB1580461A GB16691/77A GB1669177A GB1580461A GB 1580461 A GB1580461 A GB 1580461A GB 16691/77 A GB16691/77 A GB 16691/77A GB 1669177 A GB1669177 A GB 1669177A GB 1580461 A GB1580461 A GB 1580461A
- Authority
- GB
- United Kingdom
- Prior art keywords
- group
- complex
- compound
- transition metal
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 150000003624 transition metals Chemical class 0.000 title claims abstract description 20
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- XQJHRCVXRAJIDY-UHFFFAOYSA-N aminophosphine Chemical compound PN XQJHRCVXRAJIDY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 45
- 230000003287 optical effect Effects 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- -1 aminophosphino group Chemical group 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- XZKIHKMTEMTJQX-UHFFFAOYSA-N 4-Nitrophenyl Phosphate Chemical compound OP(O)(=O)OC1=CC=C([N+]([O-])=O)C=C1 XZKIHKMTEMTJQX-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 150000003623 transition metal compounds Chemical class 0.000 claims description 4
- 239000007832 Na2SO4 Substances 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 125000005110 aryl thio group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000004508 fractional distillation Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 125000004437 phosphorous atom Chemical group 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 229940116333 ethyl lactate Drugs 0.000 claims description 2
- 229940117360 ethyl pyruvate Drugs 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 230000007704 transition Effects 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000010948 rhodium Substances 0.000 description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 5
- 239000003446 ligand Substances 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 3
- 235000004279 alanine Nutrition 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- VFUFIIXSVCSRBQ-LLVKDONJSA-N (2R)-2-acetamido-3-(3-acetyloxy-4-methoxyphenyl)propanoic acid Chemical compound C(C)(=O)OC=1C=C(C[C@@H](NC(C)=O)C(=O)O)C=CC1OC VFUFIIXSVCSRBQ-LLVKDONJSA-N 0.000 description 2
- DNJSHXYKYRIMOH-SECBINFHSA-N (2r)-2-acetamido-3-(1,3-benzodioxol-5-yl)propanoic acid Chemical compound CC(=O)N[C@@H](C(O)=O)CC1=CC=C2OCOC2=C1 DNJSHXYKYRIMOH-SECBINFHSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000005418 aryl aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 2
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 2
- 239000004913 cyclooctene Substances 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- IKGHIFGXPVLPFD-NSHDSACASA-N methyl (2s)-2-acetamido-3-phenylpropanoate Chemical compound COC(=O)[C@@H](NC(C)=O)CC1=CC=CC=C1 IKGHIFGXPVLPFD-NSHDSACASA-N 0.000 description 2
- 230000002906 microbiologic effect Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- XNCRUNXWPDJHGV-BQYQJAHWSA-N (e)-2-methyl-3-phenylprop-2-enoic acid Chemical compound OC(=O)C(/C)=C/C1=CC=CC=C1 XNCRUNXWPDJHGV-BQYQJAHWSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- RIFKADJTWUGDOV-UHFFFAOYSA-N 1-cyclohexylethanone Chemical compound CC(=O)C1CCCCC1 RIFKADJTWUGDOV-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- UFDFFEMHDKXMBG-UHFFFAOYSA-N 2-acetamidoprop-2-enoic acid Chemical compound CC(=O)NC(=C)C(O)=O UFDFFEMHDKXMBG-UHFFFAOYSA-N 0.000 description 1
- WXUAQHNMJWJLTG-UHFFFAOYSA-N 2-methylbutanedioic acid Chemical compound OC(=O)C(C)CC(O)=O WXUAQHNMJWJLTG-UHFFFAOYSA-N 0.000 description 1
- MSIFHGPIEOZWQZ-UHFFFAOYSA-N 3-chlorobicyclo[2.2.1]hepta-1,3-diene;rhodium Chemical class [Rh].C1CC2=CC(Cl)=C1C2 MSIFHGPIEOZWQZ-UHFFFAOYSA-N 0.000 description 1
- MDFWXZBEVCOVIO-UHFFFAOYSA-N 4,7,7-trimethylbicyclo[2.2.1]heptan-3-amine Chemical compound C1CC2(C)C(N)CC1C2(C)C MDFWXZBEVCOVIO-UHFFFAOYSA-N 0.000 description 1
- RBMUAGDCCJDQLE-UHFFFAOYSA-N 5-methyl-2-propan-2-ylcyclohexan-1-amine Chemical compound CC(C)C1CCC(C)CC1N RBMUAGDCCJDQLE-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-UWTATZPHSA-N D-alanine Chemical compound C[C@@H](N)C(O)=O QNAYBMKLOCPYGJ-UWTATZPHSA-N 0.000 description 1
- 101000961040 Homo sapiens Atrial natriuretic peptide receptor 2 Proteins 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CBQJSKKFNMDLON-JTQLQIEISA-N N-acetyl-L-phenylalanine Chemical compound CC(=O)N[C@H](C(O)=O)CC1=CC=CC=C1 CBQJSKKFNMDLON-JTQLQIEISA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 102000002451 NPR2 Human genes 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- WZVCQMPJFZLBRX-UHFFFAOYSA-N [Pb].C(C)N(CC)CC Chemical compound [Pb].C(C)N(CC)CC WZVCQMPJFZLBRX-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052783 alkali metal Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 1
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 1
- 239000012971 dimethylpiperazine Substances 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- KTHDTJVBEPMMGL-GSVOUGTGSA-N n-acetylalanine Chemical compound OC(=O)[C@@H](C)NC(C)=O KTHDTJVBEPMMGL-GSVOUGTGSA-N 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical group 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- BXRNXXXXHLBUKK-UHFFFAOYSA-N piperazine-2,5-dione Chemical compound O=C1CNC(=O)CN1 BXRNXXXXHLBUKK-UHFFFAOYSA-N 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- OIWNHEPSSHYXTG-UHFFFAOYSA-L ruthenium(2+);triphenylphosphane;dichloride Chemical compound Cl[Ru]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 OIWNHEPSSHYXTG-UHFFFAOYSA-L 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
- C07D317/60—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- 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
- C07F15/0073—Rhodium compounds
- C07F15/008—Rhodium compounds without a metal-carbon linkage
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
- C07F9/4883—Amides or esteramides thereof, e.g. RP(NR'2)2 or RP(XR')(NR''2) (X = O, S)
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Abstract
For the asymmetrical hydrogenation of substrates selected from prochiral olefins and compounds containing CO and/or CN groups, the olefin of interest here is contacted with a complex of a transition metal with an asymmetrical aminophosphine. The asymmetrical aminophosphine is selected from those of the formula PR@(NR<2>R<3>)3-x where R<1>, R<2> and R<3> are as defined in the claims. The catalytic system as a means for carrying out the abovementioned asymmetrical hydrogenation contains a complex obtained by a reaction starting from compounds of the formula (R<3>R<2>N)nX and a coordination compound of a metal from the transition series.
Description
(54) TRANSITION METAL COMPLEXES
(71) We, SNAMPROGETTI S.P.A., an Italian Company, of Corso
Venezia 16, Milan, Italy, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to transition metal complexes and to their use as catalysts in the asymmetrical hydrogenation of prochiral and racemic ethylenically unsaturated compounds and of compounds containing CO and/or CN groups.
The preparation on an industrial scale of optically active organic compounds having high optical purity, for instance levorotatory amino acids, is almost exclusively carried out by processes of the biochemical or microbiological type.
Until recently, there were known no purely chemical processes which were able to complete with the biochemical or microbiological processes in terms of economy and optical yield. However, the discovery of new homogeneous catalytic systems having a high stereospecificity, for example tris(triphenyl-phosphine)chlororhodium, and new developments in the synthesis of phosphines containing asymmetrical phosphorus, lead.to the preparation of transition metal chiral complexes having a high stereo-selectivity in the hydrogenation of prochiral olefins.
According to the present invention, there is provided a complex of (a) a coordination compound of a transition metal and (b) an optically-active aminophosphine containing at least one chiral centre.
The aminophosphine preferably has the general formula: PRx'(NW'R"')3, wherein R' is a monovalent organic radical, x is 0, 1 or 2, and R" and R"' are the same or different and each is a monovalent organic radical at least one of which contains one or more chiral centres. Preferably, R' of the aminophosphine is an alkyl group, an aryl group, an alkylaryl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylphosphino group (as herein defined), an arylphosphino group (as herein defined) or an aminophosphino group (as herein defined), and R" and R"' of the aminophosphine are the same or different and each is an alkyl group, an aryl group, an alkylaryl group or a cycloalkyl group at least one of which contains one or more chiral centres.
The terms (1) "alkylphosphino", (2) "arylphosphino" and (3) aminophosphino" used herein mean respectively:
(1) alkyl alkyl P- or P-alkylene alkyl alkyl (2) aryl aryl P- or P-arylene aryl aryl (3) NH NHy K P- or P-NH NH2 NH2 The invention also provides a process for the preparation of a transition metal complex of the invention, which comprises reacting an optically-active aminophosphine containing at least one chiral centre with a coordination compound of a transition metal.
The invention further provides a process for the asymmetrical hydrogenation of a prochiral or racemic ethylenically unsturated compound, which comprises contacting the compound with a complex of the invention.
The invention further provides a process for the asymmetrical hydrogenation of a compound containing a CO and/or CN group, which comprises contacting the compound with a complex of the invention.
The radical NR"R" in the above general formula is an optically active amino group derived from an amino compound. Thus, the radical NR"R" may be selected from a wide category of mono- and poly-dentate ligands capable of coordinating with transition metal compounds to form complexes suitable for asymmetrical hydrogenation of prochiral and racemic olefins to produce the corresponding saturated compounds, and of compounds containing CO and/or CN groups.
The preparation of the aminophosphines can be carried out by reacting an organic amine or alkali metal derivative thereof with a halophosphine, e.g. a chlorophosphine. Thus, for example, the preparation of the aminophosphines can be carried out according to one of the following schemes:
(1) R*NH2+ R2PCI + BeR*NHPR2+ HCI (2) RR*NH+R2PCl+BRR*N-PR2+HCl (3) RR*NNa+R2PClRR*NPR2+NaCl (4) 2RR*NH+RPCI2+2B(RR*N)2PR+2B . HCI
(5) R*NH2+2R2PCI+2B < R*N(PR2)2+2B . HCI (6) RR*N),PR+ ROH-+(RR*N)PR(OR)+ RR*NH (7) 3RR*NH+PC1,+3B-(RR*N),P+3B . HCI, wherein the groups R have the above meanings and B is an organic base. The preparation can be carried out according to processes already known for the corresponding achiral compounds.
Examples of the optically active amines R*NH2 are a methylbenzylamine, bornylamine, sec.-butylamine, menthylamine or any primary amine containing one or more chiral centres. In the secondary amines R*RNH, one or both of the groups attached to the nitrogen atom can contain one or more chiral centres. Examples of such secondary amines are unsubstituted N-methyl-a-methyl-benzylamine, pipecoline, desoxyephidrine, O-substituted ephedrines, N-monosubstituted and
N,N'-disubstituted ethylenediamines with at least one chiral centre and piperazines containing one or more chiral centres.
The active catalytic complex is formed in the asymmetrical hydrogenation by reacting the aminophosphine with a coordination compound of a transition metal, preferably Cr, Mo, W, Fe, Co, Ni, Ru, Rh, Pd, Pt, Os, Ir, Cu, Ag, Au, Ti or V.
The ligands of the coordination compounds can be anionic or neutral.
Examples of anionic ligands are halogens, cyanide, nitrate, acetate, acetylacetonate and sulphide. Examples of neutral ligands are water, ammonia, amines, phosphines, carbon monoxide, olefins and diolefins. Examples of coordination compounds are rhodium(lII) hydrated chloride, ruthenium(II) chloride, dichloro-tetrakis(triphenylphosphine)ruthenium(II), rhodium(I) ,u-dichloro-tetrakis(ethylene), rhodium(I) -dichloro-bis(norbornadiene), dichloro-tetraamino-platinum(II) and dibromo-tetrakis(triphenylphosphine)palladium.
The molar ratio between the aminophosphine and the transition metal compound, as expressed as the ratio between the number of phosphorus atoms of the aminophosphine and the number of transition metal atoms, is preferably from 1:1 to 15:1, the ratios 2:1, 3:1 and 4:1 being most preferred.
The reaction solvent, if such is used, is preferably an aromatic hydrocarbon, an aliphatic hydrocarbon, an alcohol, an ether, a ketone, an ester, an amide or a mixture of two or more thereof.
The asymmetrical hydrogenation is preferably carried out at a molar ratio of substrate to catalyst of from 10,000:1 to 10:1. The reaction temperature is preferably from -70 to 2000 C., more preferably from 0 to 500 C. The hydrogen pressure is preferably in the range of 1 to 100 atmospheres.
The following Examples illustrate the invention.
EXAMPLE 1 N,N'-bis(S(-)a-methylbenzyl)ethylenediamine was prepared from S(-)amethylbenzylamine and diethyl oxalate. The diamide was reduced with lithium aluminium hydride in tetrahydrofuran (THF) and the corresponding diamine was isolated as its dihydrochloride. The latter had a melting point of 250"C and was obtained in a yield of 80%.
The dihydrochloride was treated with 10% NaOH, and 0.050 mols of the diamine thus obtained were treated with 0.100 mols of diphenylchlorophosphine in 300 ml of anhydrous benzene, in the presence of 0.200 mols of triethylamine.
The mixture was refluxed for 20 hours, the triethylammonium hydrochloride formed then being filtered off and the benzene solution being concentrated until N,N'-bis(S(-)a-methylbenzyl)-N,N'-bis(diphenylphosphino)ethylenediamine separated. The yield of product was 70% with respect to the starting diamine, and the product had a melting point of 138--140"C and an optical rotation [a]g of -91.5 (c=l in CHCl3).
A catalyst was prepared by treating 5.5 mg of rhodium(I) ,u- dichlorotetrakis(ethylene) (17.7x 10-6 mols) with 22.5 mg of N,N'-bis(S(-)a- methylbenzyl)-N,N'-bis(diphenylphosphino)ethylenediamine (35.4x 10-6 mols), 6 ml of anhydrous benzene being used as solvent. The atomic ratio P/Rh was 2.
The solution was transferred into a flask containing 2.8 g of - acetylamidocinnamic acid in 24 ml of anhydrous methanol, the flask being connected to a hydrogenating apparatus operating at atmospheric pressure and kept at 250C by a thermostat. A careful purge with hydrogen of the reaction environment was effected before the catalytic complex was added. The reaction was monitored by means of normal monitoring techniques. The initial rate of hydrogen absorption was about 4 ml/minute under the operating conditions.
After 3 hours, the conversion was about 85%. The reaction was terminated and the reaction product was separated by evaporating the solvent under reduced pressure.
The product was treated with a 0.5N NaOH solution, and the insoluble catalyst was filtered off. The aqueous solution was brought to a pH of 2-3 by the addition of dilute HCI, and the organic phase was extracted five times with ethyl ether. The ether extracts were combined and dried over Na2SO4. The ether was then evaporated. The product, according to its NMR and IR spectrographs, consisted of R(-)N-acetylphenylalanine. Its optical rotation [ce]2D was -40 (c=l in 95 /" EtOH), and the optical yield was 84%. The optical rotation [a]2D0 of enantiomerically pure
S(+)N-acetylphenyl alanine is +47.5 (c=l in 95 /" EtOH).
EXAMPLE 2
By repeating the process described in Example 1 using R(+)amethylbenzylamine, N,N' - (R(+)a - methylbenzyl) - N,N' - (diphenyl phosphino)ethylenediamine was prepared, having two centres of chirality of opposite configuration with respect to the diphosphine of Example 1.
The product was reacted with the rhodium compound used in Example 1, and the catalytic complex obtained was used in the hydrogenation of a- acetylaminocinnamic acid. The hydrogenated product was isolated and examined as in Example 1. It consisted of S(+)N-acetylphenylalanine, and had an optical rotation [a]2 of +38.9 (c=l in 95% EtOH) indicating an enantiomeric purity of 82%.
EXAMPLE 3
2(S),5(S)-dimethylpiperazine was prepared by the cyclodimerisation of S(-) alanine and reduction of the resulting diketopiperazine with lithium aluminium hydride.
The subsequent reaction of the above piperazine with diphenylchlorophosphine in the presence of triethylamine lead to the formation of 2(S),5(S)-dimethyl-N,N'-diphenylphosphino (+)-piperazine having an optical rotation [a]2D of +78 (c=l in THF), in a yield of 60%.
By the procedure of Example 1, the thus prepared product (134x10-5 mols) was reacted with rhodium(I) ,u-dichlorotetrakisfethylene) (67x 10-6 mols), and the catalytic complex obtained was used in the hydrogenation of a-acetylamidocinnamic acid (13x 10-3 mols) at 250C under atmospheric pressure. Nacetyl-(S)phenylalanine was thus obtained in a yield of 8O85%. It had an optical rotation [a]20+0.5 (c=l in 95 /n EtOH) and an optical purity of 1%.
EXAMPLE 4
A catalytic complex prepared according to Example 1 from 47.9 mg of rhodium(I) ,u-dichlorotetrakiscyclooctene (66.8x 10-5 mols) and 86 mg of N,N' (S(-)methylbenzyl)-N,N'-(diphenylphosphino)ethylenediamine (135 x 10-6 mols) was used in the catalytic hydrogenation of 3-acetoxy-4-methoxy-a- acetylamidocinnamic acid (2 g) under atmospheric pressure at 250C. By operating as described in Example 1, 3-acetoxy-4-methoxy-N-acetyl-(R)phenylalanine was isolated from the reaction medium in a yield of 85-90%. It had an optical rotation [lr]2D of -16.9 (c=l in acetone). The optical yield was 77%. Enantiometically pure 3acetoxy-4-methoxy-N-acetyl-(R)phenylalanine has an optical rotation [a]2D of -22 (c=l in acetone).
EXAMPLE 5 1-phenyl-2,5-S(-)α-methylbenzyl-1-phospha-2,5-azacylcopentane was prepared by reacting N,N'-(S(-)α-methylbenzyl)ethylenediamine with phenyldichlorophosphine in the presence of triethylamine. 380x 10-6 mols of the product were reacted with 95x 10-6 mols of rhodium(I) - dichlorotetrakis(ethylene). The P/Rh ratio was 2.
By the procedure of Example 3 the catalyst was used in the hydrogenation of acetylaminoacrylic acid, under a pressure of 15 atmospheres of hydrogen and at room temperature.
Enantiomerically pure N-acetyl-S(-)alanine was obtained in a yield of 85-90%. It had an optical rotation [a]2 of -5 (c=l in H2O). The optical yield was 7.5.
Enantiomerically pure N-acetyl-R(-)alanine has an optical rotation [cr]2D of 66.5 (c=2 in H9O).
EXAMPLE 6
A catalytic complex prepared according to Example 1 from rhodium(l) y- dichlorotetrakis(ethylene) (73x 10-6 mols) and N,N'-(S(-)cr-methylbenzyl)-N,N'- (diphenylphosphino)ethylenediamine (146x 10-8 mols) was used in the catalytic hydrogenation of 3,4-methylenedioxy-a-acetylamidocinnamic acid (6.98x10-3 mols) at 25 C under atmospheric pressure. By operating as described in Example 1, 3,4-methylenedioxy-N-acetyl(R)phenylalanine was isolated in a quantitative yield.
It had an optical rotation l]'D6 of -40 (c=1.8 in 95% EtOH). The optical yield was 75%.
Enantiomerically pure 3,4-methylenedioxy-N-acetyl-(R)phenylalanine has an optical rotation [CE]18 of -53.4 (c=1.8 in 85% EtOH).
EXAMPLE 7
A catalytic complex prepared according to Example 1 from rhodium(l) y- dichlorotetrakis(cyclooctene) (13.9x10-5 mols) and n,n'-(S(-)a-methylbenzyl)- N,N'-(diphenylphosphino)ethylenediamine (27.5x 10-8 mols) was used in the catalytic hydrogenation at 250C and under atmospheric pressure of aacetylamidoacrylic acid (15.5x 10-3 mols). There was obtained N-acetyl-(R)alanine in a quantitative yield. It had an optical rotation [a]2 of 48.5. The optical yield was 73%.
EXAMPLE 8
A catalytic complex prepared as described in Example I from rhodium (I) ,u-dichlorotetrakis(cyclooctene) (146x 10-8 mols) and n,n'-(S(-)a- methylbenzyl)-n,n'-(diphenylphosphino)ethylenediamine (278x10-5 mols), was used in the catalytic hydrogenation of the methyl ester of a-acetylamidocinnamic acid (13.7x10-3 mols). R(-)N-acetyl-phenylalanine methyl ester was isolated by chromatography on silica gel. It had an optical rotation [s]2D5 Of ~10 (c=l.9 in
MeOH). The optical yield was 46.5%.
Enantiomerically pure S(-)N-acetyl-phenylalanine methyl ester has an optical rotation [a]2D of +21.4 (c=1.9 in MeOH).
EXAMPLE 9
A catalytic complex prepared according to Example 1 from rhodium(I) ,u- dichlorotetrakis(ethylene) (77x 10-8 mols) and N,N'-(S(-)a-methylbenzyl)-N,N'- (diphenylphosphino)ethylenediamine (154x10-8 mols), was used in the catalytic hydrogenation of propene-2,3-dicarboxylic acid (15x10-3 mols) at 15.5 atmospheres and 30"C. Propane-2,3-dicarboxylic (R)acid was isolated in a quantitative yield. It had an optical rotation [a]2D of 1.5 (c=l in H2O). The optical yield was 10%.
EXAMPLE 10
A catalytic complex prepared according to Example 1 from rhodium(I) y- dichlorotetrakis(ethylene) (72x 10-6 mols) and N,N'-(S(-)a-methylbenzyl)-N,N'- diphenylphosphino)ethylenediamine (146x10-6 mols), was used in the catalytic hydrogenation of a-methylcinnamic acid at 5 atmospheres and 25"C. 2
Benzylpropionic (S)acid was recovered according to Example I in a quantitative yield. It had an optical rotation []2D of -1 (c=l in benzene). The optical yield was 4% EXAMPLE 11
7 ml of anhydrous methanol and 5 g of acetophenone were charged in an autoclave under nitrogen atmosphere. A solution of 2 ml of benzene containing 18.7 mg of rhodium chloro-norbornadiene dimer, i.e. (RhCINBD)2, and 56.3 mg of
N,N' - bis(S(-)a - methylbenzyl) - N,N' - (diphenylphosphino)ethylenediamine, i.e.
PNNP, was then added. After establishing a vacuum in the autoclave, the autoclave was charged with hydrogen to a pressure of 12 atmospheres. After 12 hours at room temperature, 4 atmospheres of hydrogen had been absorbed with a conversion of about 80%. The reaction was stopped at this time. Benzene and methanol were removed under reduced pressure, and, by fractional distillation under vacuum, 3.9 g of a product were then recovered. The NMR spectrograph of the product showed that it consisted of R(+)l-methyl-phenyl-carbinol. It had an optical rotation Ic]20 of +7.4 (pure product). Its optical purity was 17% ([sr]2D=+44.2).
EXAMPLE 12
A catalyst was prepared from 45 mg of(RhClNBD)2 and 124 mg of PNNP in 3 ml of benzene. The catalytic solution was charged into an autoclave containing 5 g of cyclohexylmethylketone in 7 ml of methanol. The autoclave was charged with hydrogen to a pressure of 12 atmospheres. After 48 hours at room temperature, about 3 atmospheres of hydrogen had been absorbed. The reaction was terminated.
In the manner described in Example 1, 3.15 g of a product were recovered. The product was R(-)l-cyclohexylethanol and had an optical rotation [(z]20 of -0.430 (pure compound). The optical yield was 8% ([a]2=-5.5).
EXAMPLE 13
A flask containing 2 ml of benzene was charged with 24.2 mg of (RhCINBD)2 and 66.8 mg of PNNP. Thereafter, 2.28 ml of diphenylsilane were added. The flask was cooled to 0 C, and 1.21 g of acetophenone-anil, i.e. C8H 8-n=C(CH3)-C8H5, in 6 ml of benzene were added dropwise. After 12 hours at OOC, 4 ml of 10% HCI and acetone were added until a homogeneous solution was obtained after filtration of the hydrolysis products. After removal of the acetone under reduced pressure, 100 ml of 5%, HCI were added, and the mixture is extracted six times with 25 ml of diethyl ether, the aqueous phase was made alkaline with 2N NaOH, and an organic phase obtained by extracting four times with 20 ml of diethyl ether was dried over
Na2SO4. The ether was then removed. The residue was distilled under vacuum to obtain 700 mg of a compound identified as R(-)N-phenyl-n-methylbenzylamine.
The product had an optical rotation [(r]2,0 of -3.29 (c=2.15 in EtOH). Its optical purity was 12.2 ' ([c]2g=26.1).
EXAMPLE 14
By the procedure described in Example 3 using a catalytic solution of 19 mg of (RhCINBD)2 and 55 mg of PNNP in 2 ml of benzene, 4.3 g of ethyl pyruvate in 10 ml of benzene were reacted with 5.79 of diphenylsilane in 5 ml of benzene. In this
Example, contrary to Example 3, the silane was added dropwise to the solution of the other reactants, which solution was kept at OOC. After 2 hours at OOC, hydrolysis was effected by means of 30 ml of MeOH containing 10 mg of ptoluenesulphonic acid. After filtration and removal of the methanol, 3.5 g of
D(+)ethyl lactate, having an optical rotation []2g of +3.25, were isolated by fractional distillation. Its optical purity was 22.4% ([a]200-14.5).
WHAT WE CLAIM IS:- 1. A complex of (a) a coordination compound of a transition metal and (b) an optically-active aminophosphine containing at least one chiral centre.
2. A complex according to claim 1, wherein the aminophosphine has the general formula: PRx'(NR"R"')x wherein R' is a monovalent organic radical, x is 0, 1 or 2, and R" and R"' are the same or different and each is a monovalent organic radical at least one or which contains one or more chiral centres.
3. A complex according to claim 2, wherein R' of the aminophosphine is an alkyl group, an aryl group, an alkylaryl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group; an alkylphosphino group (as herein defined), an arylphosphino group (as herein defined) or an aminophosphino group (as herein defined); and R" and R"' of the aminophosphine are the same or different and each is an alkyl group, an aryl group, an alkylaryl group or a cycloalkyl group at least one of which contains one or more chiral centres.
4. A process for the preparation of a transition metal complex as claimed in claim 1, which comprises reacting an optically-active aminophosphine containing at least one chiral centre with a coordination compound of a transition metal.
5. A process according to claim 4, wherein the molar ratio of aminophosphine to transition metal compound is from 1:1 to 15: 1, expressed as the ratio between the phosphorus atoms and transition metal atoms.
6. A process according to claim 4 or 5, wherein the reaction is carried out in a solvent which is an aromatic hydrocarbon, an aliphatic hydrocarbon, an alcohol, an ether, a ketone, an ester, an amide or a mixture of two or more thereof.
7. A process according to claim 4, substantially as described in any one of the foregoing Examples.
8. A transition metal complex whenever prepared by the process claimed in any of claims 4 to 7.
9. A process for the asymmetrical hydrogenation of a prochiral or racemic ethylenically unsaturated compound, which comprises contacting the compound with a complex as claimed in any of claims I to 3 and 8.
10. A process for the asymmetrical hydrogenation of a compound containing a
CO and/or CN group, which comprises contacting the compound with a complex as claimed in any of claims 1 to 3 and 8.
11. A process according to claim 9 or 10, wherein the molar ratio of compound to complex is from 10,000:1 to 10:1.
12. A process according to any of claims 9 to 11, wherein the contacting is effected at a temperature of from -70 to 2000 C.
13. A process according to claim 12, wherein the contacting is effected at a temperature of from 0 to 500 C.
14. A process according to any of claims 9 to 13, wherein the contacting is effected under a hydrogen pressure of from 1 to 100 atmospheres.
15. A process according to claim 9, substantially as described in any one of the foregoing Examples I to 10.
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (17)
1. A complex of (a) a coordination compound of a transition metal and (b) an optically-active aminophosphine containing at least one chiral centre.
2. A complex according to claim 1, wherein the aminophosphine has the general formula: PRx'(NR"R"')x wherein R' is a monovalent organic radical, x is 0, 1 or 2, and R" and R"' are the same or different and each is a monovalent organic radical at least one or which contains one or more chiral centres.
3. A complex according to claim 2, wherein R' of the aminophosphine is an alkyl group, an aryl group, an alkylaryl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group; an alkylphosphino group (as herein defined), an arylphosphino group (as herein defined) or an aminophosphino group (as herein defined); and R" and R"' of the aminophosphine are the same or different and each is an alkyl group, an aryl group, an alkylaryl group or a cycloalkyl group at least one of which contains one or more chiral centres.
4. A process for the preparation of a transition metal complex as claimed in claim 1, which comprises reacting an optically-active aminophosphine containing at least one chiral centre with a coordination compound of a transition metal.
5. A process according to claim 4, wherein the molar ratio of aminophosphine to transition metal compound is from 1:1 to 15: 1, expressed as the ratio between the phosphorus atoms and transition metal atoms.
6. A process according to claim 4 or 5, wherein the reaction is carried out in a solvent which is an aromatic hydrocarbon, an aliphatic hydrocarbon, an alcohol, an ether, a ketone, an ester, an amide or a mixture of two or more thereof.
7. A process according to claim 4, substantially as described in any one of the foregoing Examples.
8. A transition metal complex whenever prepared by the process claimed in any of claims 4 to 7.
9. A process for the asymmetrical hydrogenation of a prochiral or racemic ethylenically unsaturated compound, which comprises contacting the compound with a complex as claimed in any of claims I to 3 and 8.
10. A process for the asymmetrical hydrogenation of a compound containing a
CO and/or CN group, which comprises contacting the compound with a complex as claimed in any of claims 1 to 3 and 8.
11. A process according to claim 9 or 10, wherein the molar ratio of compound to complex is from 10,000:1 to 10:1.
12. A process according to any of claims 9 to 11, wherein the contacting is effected at a temperature of from -70 to 2000 C.
13. A process according to claim 12, wherein the contacting is effected at a temperature of from 0 to 500 C.
14. A process according to any of claims 9 to 13, wherein the contacting is effected under a hydrogen pressure of from 1 to 100 atmospheres.
15. A process according to claim 9, substantially as described in any one of the foregoing Examples I to 10.
16. A process according to claim 10, substantially as described in any one of
the foregoing Examples 11 to 14.
17. The product of a process as claimed in any of claims 9 to 16.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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IT2265376A IT1063212B (en) | 1976-04-26 | 1976-04-26 | Asymmetric hydrogenation of olefins, carbonyl cpds. or nitriles - using transition metal complex of asymmetric amino-phosphine |
IT2013977A IT1113753B (en) | 1977-02-10 | 1977-02-10 | Asymmetric hydrogenation of olefins, carbonyl cpds. or nitriles - using transition metal complex of asymmetric amino-phosphine |
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GB1580461A true GB1580461A (en) | 1980-12-03 |
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GB16691/77A Expired GB1580461A (en) | 1976-04-26 | 1977-04-21 | Transition metal complexes |
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AU (2) | AU523259B2 (en) |
CA (1) | CA1109074A (en) |
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DD (2) | DD132487A5 (en) |
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FR (1) | FR2349555A1 (en) |
GB (1) | GB1580461A (en) |
HU (2) | HUT33991A (en) |
LU (1) | LU77197A1 (en) |
NL (1) | NL180096C (en) |
NO (2) | NO771419L (en) |
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1977
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- 1977-04-19 AU AU24407/77A patent/AU523259B2/en not_active Ceased
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- 1977-04-25 DK DK180877A patent/DK180877A/en not_active Application Discontinuation
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- 1977-04-26 DE DE2759684A patent/DE2759684C2/en not_active Expired
- 1977-04-26 NL NLAANVRAGE7704570,A patent/NL180096C/en not_active IP Right Cessation
- 1977-04-26 DE DE2718533A patent/DE2718533C3/en not_active Expired
- 1977-04-26 DE DE2759683A patent/DE2759683C3/en not_active Expired
- 1977-04-26 JP JP4750177A patent/JPS52151127A/en active Granted
- 1977-10-31 NO NO773738A patent/NO773738L/en unknown
-
1983
- 1983-09-09 SE SE8304837A patent/SE460066B/en not_active IP Right Cessation
-
1984
- 1984-07-12 AU AU30546/84A patent/AU572169B2/en not_active Ceased
Also Published As
Publication number | Publication date |
---|---|
CH629166A5 (en) | 1982-04-15 |
DD132487A5 (en) | 1978-10-04 |
DE2759683B1 (en) | 1980-07-17 |
LU77197A1 (en) | 1977-08-17 |
NO771419L (en) | 1977-10-27 |
DE2718533B2 (en) | 1979-12-20 |
AU572169B2 (en) | 1988-05-05 |
NL180096C (en) | 1987-01-02 |
SE460066B (en) | 1989-09-04 |
NO773738L (en) | 1977-10-27 |
SE434918B (en) | 1984-08-27 |
SE7704738L (en) | 1977-10-27 |
DE2718533C3 (en) | 1980-08-28 |
DD137233A5 (en) | 1979-08-22 |
HUT33991A (en) | 1985-01-28 |
CA1109074A (en) | 1981-09-15 |
FR2349555B1 (en) | 1980-12-26 |
YU107577A (en) | 1983-02-28 |
JPS633871B2 (en) | 1988-01-26 |
DK180877A (en) | 1977-10-27 |
AU2440777A (en) | 1979-03-08 |
DE2718533A1 (en) | 1977-11-24 |
JPS52151127A (en) | 1977-12-15 |
AU3054684A (en) | 1984-12-20 |
DE2759683C3 (en) | 1981-10-15 |
HUT34037A (en) | 1985-01-28 |
DE2759684C2 (en) | 1986-05-28 |
SE8304837L (en) | 1983-09-09 |
AU523259B2 (en) | 1982-07-22 |
SE8304837D0 (en) | 1983-09-09 |
NL7704570A (en) | 1977-10-28 |
NL180096B (en) | 1986-08-01 |
FR2349555A1 (en) | 1977-11-25 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PS | Patent sealed [section 19, patents act 1949] | ||
732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
PCNP | Patent ceased through non-payment of renewal fee |