JP2010504964A - ヒドロシリル化 - Google Patents
ヒドロシリル化 Download PDFInfo
- Publication number
- JP2010504964A JP2010504964A JP2009530313A JP2009530313A JP2010504964A JP 2010504964 A JP2010504964 A JP 2010504964A JP 2009530313 A JP2009530313 A JP 2009530313A JP 2009530313 A JP2009530313 A JP 2009530313A JP 2010504964 A JP2010504964 A JP 2010504964A
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- JP
- Japan
- Prior art keywords
- hydrosilane
- substrate
- exposing
- catalyst
- carbene
- 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.)
- Pending
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- 238000006459 hydrosilylation reaction Methods 0.000 title description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 107
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims abstract description 91
- 238000000034 method Methods 0.000 claims abstract description 60
- 239000000758 substrate Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims description 68
- -1 alkylsilyl ether Chemical compound 0.000 claims description 29
- 150000002466 imines Chemical class 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 125000001424 substituent group Chemical group 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 20
- 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 claims description 18
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 125000001072 heteroaryl group Chemical group 0.000 claims description 11
- 125000005647 linker group Chemical group 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 8
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims 1
- 239000000047 product Substances 0.000 description 50
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 36
- 150000002576 ketones Chemical class 0.000 description 32
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- 229910000077 silane Inorganic materials 0.000 description 24
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 19
- 125000000217 alkyl group Chemical group 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 10
- 150000003333 secondary alcohols Chemical class 0.000 description 10
- 125000000753 cycloalkyl group Chemical group 0.000 description 9
- 125000005842 heteroatom Chemical group 0.000 description 9
- 150000004756 silanes Chemical class 0.000 description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- NOOLISFMXDJSKH-KXUCPTDWSA-N (-)-Menthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@H]1O NOOLISFMXDJSKH-KXUCPTDWSA-N 0.000 description 6
- 0 CC*CC(CC)(*C(C)C)c1ccccc1 Chemical compound CC*CC(CC)(*C(C)C)c1ccccc1 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical group C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
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- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000000269 nucleophilic effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 125000003158 alcohol group Chemical group 0.000 description 4
- 125000005103 alkyl silyl group Chemical group 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 239000002638 heterogeneous catalyst Substances 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N alpha-methylbenzylalcohol Natural products CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 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 3
- YKKJDGQRNMDAHT-UHFFFAOYSA-N diphenyl-bis(1-phenylethoxy)silane Chemical compound C=1C=CC=CC=1C(C)O[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)OC(C)C1=CC=CC=C1 YKKJDGQRNMDAHT-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WSNMPAVSZJSIMT-UHFFFAOYSA-N COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 Chemical compound COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 WSNMPAVSZJSIMT-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 229940116229 borneol Drugs 0.000 description 2
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005356 chiral GC Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 2
- OMJXBHDGPPKQFE-UHFFFAOYSA-N diphenyl(1-phenylethoxy)silane Chemical compound C=1C=CC=CC=1C(C)O[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 OMJXBHDGPPKQFE-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
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- 239000011859 microparticle Substances 0.000 description 2
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- 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
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
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- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- BHIFXIATEXVOQA-UHFFFAOYSA-N 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene Chemical group CC1=C(CBr)C(C)=C(CBr)C(C)=C1CBr BHIFXIATEXVOQA-UHFFFAOYSA-N 0.000 description 1
- PSPBQXQDKPILCY-UHFFFAOYSA-N 1,3-diazaspiro[4.4]nonane Chemical group C1CCCC21NCNC2 PSPBQXQDKPILCY-UHFFFAOYSA-N 0.000 description 1
- CUJPFPXNDSIBPG-UHFFFAOYSA-N 1,3-propanediyl Chemical group [CH2]C[CH2] CUJPFPXNDSIBPG-UHFFFAOYSA-N 0.000 description 1
- YNGDWRXWKFWCJY-UHFFFAOYSA-N 1,4-Dihydropyridine Chemical compound C1C=CNC=C1 YNGDWRXWKFWCJY-UHFFFAOYSA-N 0.000 description 1
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- 125000004958 1,4-naphthylene group Chemical group 0.000 description 1
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- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- OKCUCCLHQOWBDY-UHFFFAOYSA-N 2,3,5,6,7,7a-hexahydro-1h-pyrrolo[1,2-c]imidazole Chemical group C1NCN2CCCC21 OKCUCCLHQOWBDY-UHFFFAOYSA-N 0.000 description 1
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000000075 primary alcohol group Chemical group 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 125000005032 thiofuranyl group Chemical group S1C(=CC=C1)* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000009901 transfer hydrogenation reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- AKQNYQDSIDKVJZ-UHFFFAOYSA-N triphenylsilane Chemical compound C1=CC=CC=C1[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 AKQNYQDSIDKVJZ-UHFFFAOYSA-N 0.000 description 1
- BZLZKLMROPIZSR-UHFFFAOYSA-N triphenylsilicon Chemical compound C1=CC=CC=C1[Si](C=1C=CC=CC=1)C1=CC=CC=C1 BZLZKLMROPIZSR-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B47/00—Formation or introduction of functional groups not provided for in groups C07B39/00 - C07B45/00
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
●カルボニルおよびイミンのヒドロシリル化;
●シランとアルコールとの間の脱水素縮合;および
●カルボニル化合物の不斉ヒドロシリル化。
これらの方法のそれぞれは、ポリマー型カルベン触媒の存在下で、ヒドロシランと基質との反応を含む。
イミンのヒドロシリル化は、不均一系のポリ−NHC触媒によって触媒された。ケトンのヒドロシリル化反応は、ポリ−NHC触媒系において非常に良好に機能したので、発明者らは、この系をイミンのヒドロシリル化に適用した(図5)。最初にTHFを溶媒として使用し、反応を行ったが、しかし、あいにく反応は、効率的に進行しなかった。DMFを、次にこの反応のための溶媒として試した。溶媒としてDMFを使用すると、アミン生成物は高収率を達成した。2(基質に対し10モル%)を、DMF中に懸濁した、そして次に、ジフェニルシランおよびN−(4−メトキシフェニル)−N−(1−フェニルエチル)イミン(ジフェニルシランに対し1モル当量)を、反応バイアルに加えた。反応混合物を、室温で一晩攪拌し、そして生成物をGC−MSおよびNMRによって明らかにした。N−(4−メトキシフェニル)−N−(1−フェニルエチル)アミン4は、定量的な収率の唯一の生成物であった。この反応のメカニズムは、ケトンのヒドロシリル化と同じであると考えられた。シランを、NHCによって最初に活性化し、続いて、イミンによって還元した。
ケトンの不斉ヒドロシリル化:第二級アルコールによって、キラリティーを誘導した。ほとんど全ての不斉ヒドロシリル化反応が、キラル触媒による触媒作用に依存しており、キラルシランは、これらの調製が困難であることにより、ほとんど使用されてこなかった。不斉ヒドロシリル化におけるキラルシランの使用は、今日まで報告されなかった。発明者らは、ヒドロシランと、アルコール類との縮合を通してキラルシランを生成する非常に単純で、かつ安価な方法を開発した。キラルシランを、次に不斉ヒドロシリル化反応において直接使用して、生成物においてキラリティーを誘起した(図6)。
ケトンおよびイミンのヒドロシリル化;全ての反応を、不活性雰囲気下で行った。表1のエントリー4では、グローブボックス中で攪拌棒を用いて、2(5mg)を、10mlのバイアル中でTHF中に懸濁した。ジフェニルシラン(0.2mmol、37.1μl)および4−メトキシアセトフェノン(0.2mmol、24.5μl)を、反応バイアルに加えた。反応を、室温で24時間攪拌した。ジフェニル(1−(4−メトキシフェニル)エトキシ)シラン(MS、M+:334、1H NMR(C6D6)、δ:7.7(m、2H)57.2〜7.4(m、10H)、6.9(d、2H)、5.85(s、IH)、5.1(q、IH)、3.4(s、3H)、1.6(d、3H))は、GC/MSおよびNMR分析に基づいて、定量的な収率の唯一の生成物であった。
bGCおよびGCMSによって決定した収率。
Claims (22)
- カルベン触媒の存在下で、基質を、ヒドロシランに曝すことを含む、基質を生成物に転化する方法。
- 該曝すステップが、ポリマー型カルベン触媒の存在下で、該基質を、該ヒドロシランに曝すことからなる、請求項1に記載の方法。
- 該曝すステップが、該カルベン触媒の存在下で、カルボニル化合物、イミンおよびアルコールからなる群から選択された基質を、該ヒドロシランに曝すことから成る、請求項1または請求項2の方法。
- 該方法が、該基質を、シリルエーテルおよびアミンからなる群から選択された生成物に転化する方法である、請求項1〜3のいずれか一項に記載の方法。
- 該方法が、該基質を、少なくとも約25%の鏡像体過剰率を有する生成物に転化する方法であり、該曝すステップが、該カルベン触媒の存在下で、該基質を、キラルヒドロシランに曝すことから成る、請求項1〜4のいずれか一項に記載の方法。
- 該曝すステップが、該カルベン触媒の存在下で、該基質を、モル基準で、該基質量の約100%の量の該ヒドロシランに曝すことを含んで成る、請求項1〜5のいずれか一項に記載の方法。
- 該曝すステップが、主鎖ポリマー型カルベンの存在下で、該基質を、該ヒドロシランに曝すことを含んで成る、請求項1〜6のいずれか一項に記載の方法。
- 該曝すステップが、ポリマー型主鎖N−複素環カルベンの存在下で、該基質を、該ヒドロシランに曝すことを含んで成る、請求項7に記載の方法。
- 該曝すステップが、該カルベン触媒の存在下で、該基質を、該ヒドロシランに曝すことを含んで成り、該触媒中の活性部位の該基質に対する比率が、モル基準で約1%〜約20%であるような量で、該触媒が存在する、請求項1〜9のいずれか一項に記載の方法。
- 次の反応において、該カルベン触媒を再使用することをさらに含む、請求項1〜10のいずれか一項に記載の方法。
- 該カルベン触媒が溶解できない溶媒中における該カルベン触媒の存在下で、該基質を、該ヒドロシランに曝すことを、該曝すステップが含んで成る、請求項1〜11のいずれか一項に記載の方法。
- 生成物を分離することをさらに含んで成る、請求項1〜12のいずれか一項に記載の方法。
- 該方法が、カルボニル化合物をヒドロシリル化するための方法であり、そして該曝すステップが、ポリマー型カルベン触媒の存在下で、該カルボニル化合物を、該ヒドロシランに曝すことを含んで成る、請求項1〜13のいずれか一項に記載の方法。
- 該曝すステップが、該ポリマー型カルベン触媒の存在下で、該カルボニル化合物を、キラルアルコキシヒドロシランに曝すことを含んで成る、請求項14に記載の方法。
- 該ポリマー型カルベン触媒の存在下で、キラルアルコールと、ジヒドロシランとを反応させて、該キラルアルコキシヒドロシランを生成させるステップを含む、請求項15の方法。
- 該曝すステップが、該キラルアルコキシヒドロシランの分離無しに行われる、請求項16に記載の方法。
- 該方法が、アルコールをヒドロシリル化するための方法であり、そして該曝すステップが、ポリマー型カルベン触媒の存在下で、該アルコールを、該ヒドロシランに曝すことを含んで成る、請求項1〜13のいずれか一項に記載の方法。
- 該方法が、イミンを還元するための方法であり、そして該曝すステップが、ポリマー型カルベン触媒の存在下で、該イミンを、該ヒドロシランに曝すことを含んで成る、請求項1〜13に記載の方法。
- カルベン触媒の存在下で、基質を、ヒドロシランに曝すことを含む方法によって製造される生成物。
- 該曝すステップが、ポリマー型カルベン触媒の存在下で、カルボニル化合物、イミンまたはアルコールを、該ヒドロシランに曝すことを含んで成り、該生成物が、シリルエーテルまたはアミンである、請求項20に記載の生成物。
- 該生成物が、キラルアルキルシリルエーテルである、請求項20または請求項21の生成物。
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