CN114478608A - Silicon-center chiral aryl silane and preparation method thereof - Google Patents
Silicon-center chiral aryl silane and preparation method thereof Download PDFInfo
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- CN114478608A CN114478608A CN202210045551.4A CN202210045551A CN114478608A CN 114478608 A CN114478608 A CN 114478608A CN 202210045551 A CN202210045551 A CN 202210045551A CN 114478608 A CN114478608 A CN 114478608A
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- -1 aryl silane Chemical compound 0.000 title claims abstract description 58
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 23
- 125000002541 furyl group Chemical group 0.000 claims abstract description 12
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 12
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 9
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 7
- JJXPTUWJVQUHKN-UHFFFAOYSA-N 5-methoxy-1-benzofuran Chemical compound COC1=CC=C2OC=CC2=C1 JJXPTUWJVQUHKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 125000001725 pyrenyl group Chemical group 0.000 claims abstract description 6
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims abstract description 5
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims abstract description 5
- 150000002367 halogens Chemical group 0.000 claims abstract description 5
- 150000003568 thioethers Chemical class 0.000 claims abstract description 5
- 125000002023 trifluoromethyl group Chemical class FC(F)(F)* 0.000 claims abstract description 5
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical compound CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 claims abstract description 4
- QENGPZGAWFQWCZ-UHFFFAOYSA-N Methylthiophene Natural products CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000004665 trialkylsilyl group Chemical group 0.000 claims abstract description 3
- 239000010948 rhodium Substances 0.000 claims description 30
- 239000003446 ligand Substances 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 11
- 229910052703 rhodium Inorganic materials 0.000 claims description 10
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 8
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 7
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 claims description 4
- QUGUFLJIAFISSW-UHFFFAOYSA-N 1,4-difluorobenzene Chemical compound FC1=CC=C(F)C=C1 QUGUFLJIAFISSW-UHFFFAOYSA-N 0.000 claims description 4
- 125000006705 (C5-C7) cycloalkyl group Chemical group 0.000 claims description 3
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 3
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- XMSZANIMCDLNKA-UHFFFAOYSA-N methyl hypofluorite Chemical group COF XMSZANIMCDLNKA-UHFFFAOYSA-N 0.000 claims description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 8
- 239000010703 silicon Substances 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 150000003377 silicon compounds Chemical class 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 99
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 48
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 46
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 46
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 46
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 23
- 238000005160 1H NMR spectroscopy Methods 0.000 description 23
- 238000004128 high performance liquid chromatography Methods 0.000 description 23
- 239000003208 petroleum Substances 0.000 description 23
- 238000010898 silica gel chromatography Methods 0.000 description 23
- 238000000132 electrospray ionisation Methods 0.000 description 22
- 229940125898 compound 5 Drugs 0.000 description 21
- 239000012230 colorless oil Substances 0.000 description 20
- 239000000460 chlorine Substances 0.000 description 13
- 239000000758 substrate Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000004293 19F NMR spectroscopy Methods 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000004296 chiral HPLC Methods 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000002444 silanisation Methods 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical class [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical group C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 1
- IGRCWJPBLWGNPX-UHFFFAOYSA-N 3-(2-chlorophenyl)-n-(4-chlorophenyl)-n,5-dimethyl-1,2-oxazole-4-carboxamide Chemical compound C=1C=C(Cl)C=CC=1N(C)C(=O)C1=C(C)ON=C1C1=CC=CC=C1Cl IGRCWJPBLWGNPX-UHFFFAOYSA-N 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- PWRLJYUETHNNFL-UHFFFAOYSA-N 5-(methoxymethyl)bicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(COC)CC1C=C2 PWRLJYUETHNNFL-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241001120493 Arene Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 101000652482 Homo sapiens TBC1 domain family member 8 Proteins 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910008045 Si-Si Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910006411 Si—Si Inorganic materials 0.000 description 1
- 102100030302 TBC1 domain family member 8 Human genes 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000006254 arylation reaction Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000011208 chromatographic data Methods 0.000 description 1
- 238000002983 circular dichroism Methods 0.000 description 1
- 238000001142 circular dichroism spectrum Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000010596 desymmetrization reaction Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
- 238000007086 side reaction Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 238000000547 structure data Methods 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000002424 x-ray crystallography Methods 0.000 description 1
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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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0896—Compounds with a Si-H linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
Abstract
The invention belongs to the field of chiral silicon compounds, and discloses a silicon-centered chiral aryl silane which has a structure shown in a general formula I:
wherein R is1Selected from alkyl, cycloalkyl, 2, 6-dimethylphenyl; r2Is selected from phenyl, naphthyl, pyrenyl, 2, 3-dihydrobenzofuranyl, or phenyl substituted by alkyl, alkoxy, halogen and trialkylsilyl; ar is selected from phenyl, naphthyl, furyl, 2-methylthiophene, benzofuryl, benzothienyl, 5-methoxybenzofuran, alkyl, benzyl, trimethylsilyl, thioether, phenyl-substituted furyl, alkyl, trifluoromethyl, halogen-substituted phenyl. The invention also discloses a preparation method of the silicon-center chiral aryl silane. The invention has high reaction yield, good chemical selectivity, regioselectivity and stereoselectivity, greatly expands the range of the silicon center chiral silane compound, and converts the obtained compound intoThe corresponding polymer can be used as a novel silicon-based chiral material in many fields.
Description
Technical Field
The invention belongs to the field of chiral silicon compounds, and particularly relates to silicon-center chiral aryl silane and a preparation method thereof.
Background
In recent years, chiral organosilanes have attracted increasing attention due to their unique chemical, physical, biological and stereoelectronic properties, which have potential application values in the fields of synthetic chemistry, pharmaceutical chemistry, agricultural chemistry, and material science. At present, chiral organosilane is mainly obtained through optical and kinetic resolution by adding equivalent chiral auxiliary agent, and a method for directly constructing silicon center chiral silane through catalytic asymmetric reaction is lacked. In the past decade, transition metal catalyzed desymmetrization of dihydrosilanes is an effective strategy for the synthesis of silicon-centered chirality, and selective functionalization of the Si-H bond of dihydrosilanes to silicon-centered chiral monohydroxysilanes is the most straightforward and efficient chemical synthesis method.
The prior art discloses an asymmetric reaction of intramolecular aryl C-H silanization, cyclic aryl silane is obtained with a high ee value, in order to further expand a compound molecular library of silicon center chiral aryl silane, it is necessary to develop a de-symmetrization strategy of dihydro silane to realize intermolecular enantioselective arylation reaction, compared with intramolecular reaction, the intermolecular reaction has the problem that chiral control is difficult to realize, so that the ee value is lower, firstly, because the reactivity of intermolecular C-H bond activation is low, the regioselectivity is poor, and the formation of an acyclic Si- [ Rh ] -C intermediate is difficult; secondly, the influence of the side reaction of the dihydrosilane makes the chemical selectivity difficult to control, and thirdly, the conformation of the aryl silane product generated by the intermolecular reaction is more flexible, so that the stereoselectivity of the reaction is difficult to control. Due to the difficulties, an effective synthesis method of intermolecular silicon-center chiral aryl silane is lacking.
Disclosure of Invention
The invention aims to provide a silicon-centered chiral aryl silane compound with a novel structure.
The invention also aims to provide a preparation method of the compound.
In order to achieve one of the purposes, the invention adopts the following technical scheme:
a silicon-centered chiral aryl silane having the structure of formula i:
wherein R is1Selected from alkyl, cycloalkyl, 2, 6-dimethylphenyl;
R2is selected from phenyl, naphthyl, pyrenyl, 2, 3-dihydrobenzofuranyl, or phenyl substituted by alkyl, alkoxy, halogen and trialkylsilyl;
ar is selected from phenyl, naphthyl, furyl, 2-methylthiophene, benzofuryl, benzothienyl, 5-methoxybenzofuran, alkyl, benzyl, trimethylsilyl, thioether, phenyl-substituted furyl, alkyl, trifluoromethyl, halogen-substituted phenyl.
Further, said R1Selected from (C1-C4) alkyl, (C5-C7) cycloalkyl and 2, 6-dimethylphenyl.
Further, said R1Selected from (C3-C4) alkyl, (C5-C7) cycloalkyl and 2, 6-dimethylphenyl.
Further, said R1Selected from methyl, tert-butyl, isopropyl, cyclohexyl and 2, 6-dimethylphenyl.
Further, said R1Selected from tert-butyl, isopropyl, cyclohexyl and 2, 6-dimethylphenyl.
Further, said R2Is selected from phenyl, naphthyl, pyrenyl, 2, 3-dihydrobenzofuranyl, or phenyl substituted by (C1-C4) alkyl, (C1-C4) alkoxy, halogen and trimethylsilyl.
Further, said R2Is selected from phenyl, naphthyl, pyrenyl, 2, 3-dihydrobenzofuranyl, or phenyl substituted by methyl, methoxy, fluorine and trimethylsilyl.
Further, said R2Selected from phenyl, 2-naphthyl, 1-pyrenyl, 4-methylphenyl, 4-methoxyphenyl, 4-trimethylsilylphenyl, 4-fluorophenyl, phenyl, naphthyl, or the like,
Further, Ar is selected from phenyl, naphthyl, furyl, 2-methylthiophenyl, benzofuryl, benzothienyl, 5-methoxybenzofuranyl, or (C1-C4) alkyl, benzyl, trimethylsilyl, iPrSCH2-, phenyl-substituted furyl or (C1-C4) alkyl, trifluoromethyl, halogen-substitutedA phenyl group of (a).
Further, Ar is selected from phenyl, 2-naphthyl and one of the following substituents:
further, the silicon-centered chiral aryl silane is selected from one of the following compounds:
a preparation method of silicon-centered chiral heteroaryl silane comprises the following steps: in the presence of a chiral ligand and a rhodium catalyst, the compound of formula 1 and the compound of formula 2 are reacted as follows
The rhodium catalyst is [ Rh (cod) Cl]2、[Rh(cod)OH]2、[Rh(nbd)Cl]2Or [ Rh (CO) ]2Cl]2；
The chiral ligand is selected from the following compounds:
r, R' are each independently selected from the group consisting of tert-butyl, cyclohexyl, phenyl, 2-methylphenyl, 4-trifluoromethylphenyl, 3, 5-dimethylphenyl, 3, 5-dimethyl-4-methoxyphenyl, 3, 5-di-tert-butyl-4-methoxyphenyl;
R1、R2ar is as defined above.
Further, the chiral ligand is selected from the following compounds:
further, the reaction adds cyclohexene, NBE or NBE-OMe as hydrogen acceptor.
Further, the amount of the chiral ligand is at least 3 mol%, the amount of the rhodium catalyst is at least 1 mol%, and the amount of the hydrogen acceptor is at least 100 mol%; the amounts of the ligand, rhodium catalyst and hydrogen acceptor used are based on the amount of the compound of formula 2 used as a starting material, for example, the amount of the ligand is written in the form of 4.4 mol%, meaning that 0.044mol of the ligand is used per 1mol of the compound of formula 2; the amount of the rhodium catalyst used is written in the form of 2 mol%, meaning that 0.02mol of the rhodium catalyst is used per 1mol of the compound of formula 2.
Further, the molar ratio of the compound of formula 1 to the compound of formula 2 is (1-3): 1.
further, the reaction uses toluene, benzene, naphthalene, m-xylene, 1, 3-bis (trifluoromethyl) benzene or 1, 4-difluorobenzene as a solvent.
Further, the temperature of the reaction is 20 ℃ or higher.
Further, the reaction time is at least 24 h.
As used herein, "alkyl" refers to a saturated aliphatic hydrocarbon group which is a straight or branched chain group containing 1 to 20 carbon atoms, preferably an alkyl group containing 1 to 12 carbon atoms, more preferably an alkyl group containing 1 to 6 carbon atoms. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, isopentyl, neopentyl, hexyl, 2-hexyl, 3-methylpentyl.
As used herein, "alkoxy" refers to-O- (alkyl) and-O- (cycloalkyl), where alkyl, cycloalkyl are defined herein, and non-limiting examples of alkoxy include: methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, pentyloxy, 2-pentyloxy, isopentyloxy, neopentyloxy, hexyloxy, 2-hexyloxy, 3-methylpentyloxy, cyclopropyloxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy. Alkoxy groups typically have 1 to 7 carbon atoms connected by an oxygen bridge. Alkoxy also includes substituted alkoxy. Alkoxy groups may be optionally substituted one or more times with halo.
As used herein, "cycloalkyl" refers to a non-aromatic carbocyclic ring, typically having from 3 to 8 ring carbon atoms. The rings may be saturated or have one or more carbon-carbon double bonds. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl or cycloheptyl.
As used herein, "halogen" refers to fluorine, chlorine, bromine and iodine.
"benzyl" as used herein refers to C6H5CH2-。
As used herein, "thioether" refers to (alkyl) -S- (alkyl) groups, wherein alkyl is as defined herein.
The "substitution" of the "substituted phenyl" as defined herein may be mono-substituted or poly-substituted, and "substituted phenyl" includes: (1) the benzene ring has a substituent; (2) the benzene ring has two or more substituents which may be the same or different. The substituted position may be any of positions of benzene rings 2,3, 4, 5, 6.
As used herein, a "substituted furyl" may be mono-or poly-substituted, and "substituted furyl" includes: (1) the furan ring has a substituent; (2) the furan ring has two or more substituents which may be the same or different. The substituted position may be any position of furan rings 2,3, 4.
The invention has the following beneficial effects:
the invention is the first reaction for synthesizing the chiral aryl silane by the C-H silanization of enantioselective molecules, and synthesizes the aryl silane with silicon center chirality by the intermolecular Si-H/C-H cross coupling of enantioselectivity catalyzed by chiral rhodium, and the invention has the advantages of high yield, good chemical selectivity, regioselectivity and stereoselectivity, and greatly expands the range of the silicon center chiral silane compound.
The aryl silane can be used as a key component in the field of organic functional materials, for example, the tetraaryl silane is applied to a deep blue organic electrophosphorescent device with the ultrahigh energy gap. The compound of the invention has novel structure, and the prior art does not disclose a synthesis method of the chiral silicon compound with aromatic ring and heterocycle, which can be used as a novel chiral aryl silicon framework to be applied to the field of organic functional materials.
Drawings
Figure 1 is the crystal structure of compound 5t of example 20.
Detailed Description
Carrying out conventional reaction under the conditions of argon protection and magnetic stirring; the catalytic reaction was carried out in a 10mL microwave reaction tube under the protection of argon. Obtained from the Inert Pure Solv solvent purification system or purchased anhydrous solvent from Energy Chemical. All reagents were obtained from commercial suppliers (Bide Pharmatech, Alantin, Energy Chemical, Adamas-beta and TCI) without specific indication and used without further purification. Dihydrosilane substrates were prepared by literature methods (j.am. chem. soc.2021,143, 5301-5307). Nmr spectra data were recorded using Bruker DPX 400 or Bruker DPX 600 instruments.1Chemical shifts of H NMR (400 or 600MHz) were referenced to tetramethylsilane signal (TMS: δ 0 ppm).1Chemical shifts of C NMR (100 or 150MHz) Using CDCl3As internal standard (CDCl)3: δ 77.0 ppm). High resolution mass spectral data (HRMS) were recorded on an Agilent Technologies 6230 TOF LC/MS under electrospray ionization (ESI) conditions. X-ray single crystal diffraction data were collected using Bruker D8 VENTURE. The absorption spectrum was measured with an ultraviolet-visible spectrophotometer (Shimadzu, UV 3600). The emission spectra were measured with a Shimadzu RF-6000 spectrometer. The Circular Polarized Luminescence (CPL) spectra were measured with a JASCO CPL-300 spectrometer. Circular Dichroism (CD) spectra were measured with an appied photohysics chiralscan CD spectrometer. Chiral HPLC chromatographic data were recorded using an Agilent 1260 system. In CHCl at a concentration of 0.1g/100mL3In (1), the optical rotation was measured by Rudolph automated polarimeter.
Example 1
The inventors speculate that the sterically hindered dihydrosilanes, which carry bulky groups on the dihydrosilane: (1) enhancing the stereoselective control of the chiral Rh catalyst on the removal of the symmetric oxidation addition of Si-H bonds to form a silicon chiral center; (2) inhibiting the competitive reaction of Si- [ Rh ] intermediate with dihydrosilane to form Si-Si or Si-C by-product; (3) racemization of the newly formed chiral monohydrosilane is avoided.
Reaction conditions are as follows: 1a (0.2mmol), 4a (0.1mmol), [ Rh (cod) Cl]2(2 mol%), ligand (4.4 mol%), in 1.0mL toluene under protection of argon, at 40 deg.C for 24 hours, and1h NMR determination of the yield using CH2Br2As an internal standard, the isolated yields are in parentheses; chiral HPLC determines the ee value.
| Ligands | H2Receptors | Yield (%) | ee(％) | |
| 1 | L1 | — | 8 | 89 |
| 2 | L1 | NBE | 65 | 88 |
| 3 | L1 | NBE-OMe | 73(70) | 90 |
| 4 | L2 | NBE-OMe | 23 | 72 |
| 5 | L3 | NBE-OMe | 18 | 67 |
| 6 | L4 | NBE-OMe | 31 | 85 |
| 7 | L5 | NBE-OMe | 36 | 74 |
| 8 | L6 | NBE-OMe | 42 | 51 |
| 9 | L7 | NBE-OMe | 40 | 84 |
2-Methylfuran 4a and tert-butylphenyl-substituted dihydrosilane 1a as substrates, using [ Rh (cod) Cl]2As a catalyst, Josiphos L1 as a chiral ligand, in a toluene solvent at 40 ℃, the alpha position of furan is subjected to C-H silicification reaction to obtain a chiral aryl silane product 5 a. The chiral monohydroxysilane of the heterocyclic skeleton is a compound with potential application value and can be used as a monomer for constructing a novel silicon-based chiral material.
In order to further improve the reactivity of the substrate under mild reaction conditions, a hydrogen acceptor cyclohexene or Norbornene (NBE) is added into the reaction system. When NBE was added to the reaction, product 5a was obtained in 65% yield in 88% ee, and NBE-OMe (5- (methoxymethyl) bicyclo- [2.2.1] hept-2 ene) was used as a hydrogen acceptor for the convenience of purification of the product, without affecting yield and enantioselectivity. The reaction was less efficient by using other Josiphos ligands such as L2, L3. Besides Josiphos ligands, bidentate P-N ligands Fe-PHOX L4 and chiral bisphosphine ligands such as Segphos L5 and BINAP L6, and (R, R) -iPr-BPE L7 are also suitable.
Silica gel column chromatography (petroleum ether) afforded 5a as a colorless oil (17.0mg, 70% yield), 90% ee. HPLC conditions: a Daicel Chiralpak OD-H column (n-hexane/isopropanol 100/0, 0.5mL/min) was used, with a lambda of 250nm, at a temperature of 28 ℃ and tr(minor)＝9.1min,tr(major)＝9.7min。
[α]D 25.4＝-16(c＝0.1,CHCl3)。
1H NMR(600MHz,CDCl3):δ＝7.65(d,J＝7.0Hz,2H),7.40(t,J＝7.1Hz,1H),7.36(t,J＝7.3Hz,2H),6.69(d,J＝3.0Hz,1H),6.00(d,J＝2.9Hz,1H),4.59(s,1H),2.36(s,3H),1.04(s,9H)ppm。
13C NMR(150MHz,CDCl3):δ＝157.6,151.9,135.6,132.9,129.6,127.7,124.8,105.9,27.0,17.5,13.8ppm。
HRMS (ESI) accurate mass calculation of C15H21OSi[M+H]+245.1356, found 245.1360.
General reaction conditions (step C): in an argon glove box, dihydrosilane substrate 1(0.2mmol, 2.0equiv) and heterocyclic substrate 2(0.1mmol, 1.0equiv) were added to [ Rh (cod) Cl]2(1.0mg, 2 mol%) and L1(2.4mg, 4.4 mol%) in toluene (1.0mL) were added NBE-OMe (0.1mmol, 1.0equiv), the microwave reaction tube was sealed and removed from the glove box, and the mixture was stirred at 40 ℃ for 24 hours. After completion of the reaction, the solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography to obtain a product.
After achieving the above optimal reaction conditions, the inventors expanded the substrate to substituted aromatic hydrocarbons, building acyclic aryl monosilicon-centered chiral silanes. The different substituted (hetero) arenes, including alkyl, benzyl, trimethylsilyl, thioether, phenyl substituted furans and 2-methylthiophenes, give the product in high yields (52-86%) and excellent enantioselectivities (80-90% ee). Benzofuran and benzothiophene are also suitable substrates, except furan and thiophene heterocyclic compounds, when aromatic rings such as benzene, naphthalene, m-xylene, 1, 3-bis (trifluoromethyl) benzene, 1, 4-difluorobenzene and the like are used as substrates, (R, R) -iPr-BPE is used as a ligand, the corresponding aryl silane can be obtained with the yield of 25-54% and the enantioselectivity of 31-68% ee. The substituent on the aromatic ring of the dihydrosilane compound 1 has little influence on the reaction, and both the electron-withdrawing substituent and the electron-donating substituent are feasible, so that the product is obtained with the yield of 52-67% and the ee of 80-90%. If tert-butyl is replaced by methyl, isopropyl or cyclohexyl, both the yield and the ee-value decrease.
Example 2
Compound 5 b.
Synthesized according to step C, and 5b was obtained as a colorless oil (17.1mg, 66% yield) by silica gel column chromatography (petroleum ether) in 90% ee. HPLC conditions: a Daicel Chiralpak OD-H column (n-hexane/isopropanol 100/0, 0.5mL/min) was used, with a lambda of 250nm, at a temperature of 28 ℃ and tr(minor)＝8.7min,tr(major)＝9.3min。
[α]D 25.6＝-12(c＝0.1,CHCl3)。
1H NMR(400MHz,CDCl3):δ＝7.67–7.62(m,2H),7.43–7.33(m,3H),6.57(s,1H),4.56(s,1H),2.25(s,3H),1.94(s,3H),1.04(s,9H)ppm。
13C NMR(100MHz,CDCl3):δ＝153.1,150.2,135.6,133.1,129.5,127.7,127.3,114.2,27.0,17.4,11.8,9.7ppm。
HRMS (ESI) accurate mass calculation of C16H23OSi[M+H]+259.1513, found 259.1511.
Example 3
Compound 5 c.
Synthesized according to step C, and 5C was obtained as a colorless oil (22.0mg, 73% yield) by silica gel column chromatography (petroleum ether) in 90% ee. HPLC conditions: a Daicel Chiralpak IC column (n-hexane/isopropanol 100/0, 0.5mL/min) was used, with a lambda of 250nm, at 28 ℃ and tr(major)＝8.1min,tr(minor)＝8.7min。
[α]D 25.4＝-47(c＝0.1,CHCl3)。
1H NMR(400MHz,CDCl3):δ＝7.54(d,J＝7.9Hz,2H),7.18(d,J＝7.5Hz,2H),6.67(d,J＝3.1Hz,1H),5.99(d,J＝3.1Hz,1H),4.56(s,1H),2.68(t,J＝7.5Hz,2H),2.36(s,3H),1.70–1.60(m,2H),1.43–1.33(m,2H),1.03(s,9H),0.96–0.91(m,3H)ppm。
13C NMR(100MHz,CDCl3):δ＝161.9,151.9,139.5,135.7,129.3,128.6,124.4,104.9,30.2,27.9,27.0,22.2,21.5,17.5,13.8ppm。
HRMS (ESI) accurate mass calculation of C19H29OSi[M+H]+301.1982, found 301.1982.
Example 4
Compound 5 d.
Synthesized according to step C, 5d obtained as a colorless oil (20.8mg, 62% yield), 88% ee by silica gel column chromatography (petroleum ether). HPLC conditions: two consecutive Daicel Chiralpak OD-3 columns (n-hexane/isopropanol 100/0, 0.5mL/min) were used, lambda 250nm, temperature 28 ℃, tr(minor)＝28.2min,tr(major)＝29.5min。
[α]D 25.4＝-55(c＝0.1,CHCl3)。
1H NMR(400MHz,CDCl3):δ＝7.52(d,J＝7.9Hz,2H),7.33–7.27(m,2H),7.26–7.20(m,3H),7.17(d,J＝7.5Hz,2H),6.68(d,J＝3.1Hz,1H),5.99(d,J＝3.1Hz,1H),4.56(s,1H),4.03(s,2H),2.35(s,3H),1.01(s,9H)ppm。
13C NMR(100MHz,CDCl3):δ＝159.9,153.0,139.5,138.2,135.7,129.0,128.7,128.6,128.4,126.4,124.5,106.5,34.7,26.9,21.5,17.5ppm。
HRMS (ESI) accurate mass calculation of C22H27OSi[M+H]+335.1826, found 335.1824.
Example 5
Compound 5 e.
Referring to the synthesis of step C (reaction at rt for 48h), 5e was obtained as a colorless oil by silica gel column chromatography (petroleum ether) (20.3mg, 64% yield), 84% ee. HPLC conditions: a Daicel Chiralpak IC column (n-hexane/isopropanol 100/0, 0.5mL/min) was used, lambda 250nm, at 28 ℃ and tr(major)＝7.1min,tr(minor)＝7.5min。
[α]D 25.8＝-51(c＝0.1,CHCl3)。
1H NMR(400MHz,CDCl3):δ＝7.55(d,J＝7.9Hz,2H),7.19(d,J＝7.5Hz,2H),6.74(d,J＝3.2Hz,1H),6.63(d,J＝3.2Hz,1H),4.61(s,1H),2.36(s,3H),1.04(s,9H),0.28(s,9H)ppm。
13C NMR(100MHz,CDCl3):δ＝165.7,158.4,139.5,135.7,129.1,128.6,123.1,119.1,26.9,21.5,17.6,-1.6ppm。
HRMS (ESI) accurate mass calculation of C18H29OSi2[M+H]+317.1751, found 317.1750.
Example 6
Compound 5 f.
Synthesized according to step C, and 5f was obtained as a colorless oil (27.4mg, 86% yield) by silica gel column chromatography (petroleum ether) in 90% ee. HPLC conditions: a Daicel Chiralpak IC column (n-hexane/isopropanol 100/0, 0.5mL/min) was used, lambda 250nm, at 28 ℃ and tr(major)＝13.2min,tr(minor)＝15.1min。
[α]D 26.0＝-76(c＝0.1,CHCl3)。
1H NMR(400MHz,CDCl3):δ＝7.69–7.62(m,2H),7.43–7.34(m,3H),6.71(d,J＝3.2Hz,1H),6.21(d,J＝3.2Hz,1H),4.59(s,1H),3.80(s,2H),2.96–2.85(m,1H),1.28–1.24(m,6H),1.05(s,9H)ppm。
13C NMR(100MHz,CDCl3):δ＝157.9,153.3,135.6,132.6,129.6,127.7,124.7,107.1,34.7,27.3,26.9,23.1,17.5ppm。
HRMS (ESI) accurate mass calculation of C18H27OSSi[M+H]+319.1546, found 319.1547.
Example 7
5g of compound.
Synthesized according to step C, and 5g was obtained as a colorless oil (24.7mg, yield 81%) by silica gel column chromatography (petroleum ether) in 80% ee. HPLC conditions: a Daicel Chiralpak OD-H column (n-hexane/isopropanol 100/0, 0.5mL/min) was used, with a lambda of 250nm, at a temperature of 28 ℃ and tr(minor)＝15.5min,tr(major)＝17.6min。
[α]D 25.7＝-174(c＝0.1,CHCl3)。
1H NMR(400MHz,CDCl3):δ＝7.76–7.67(m,4H),7.43–7.35(m,5H),7.30–7.25(m,1H),6.85(d,J＝3.3Hz,1H),6.69(d,J＝3.3Hz,1H),4.67(s,1H),1.10(s,9H)ppm。
13C NMR(100MHz,CDCl3):δ＝158.9,153.7,135.7,132.5,130.9,129.7,128.7,127.8,127.5,125.6,124.1,105.2,27.0,17.6ppm。
HRMS (ESI) accurate mass calculation of C20H23OSi[M+H]+307.1513, found 307.1512.
Example 8
Compound 5 h.
Referring to the synthesis of step C (reaction 48h at rt), obtained by silica gel column chromatography (petroleum ether) for 5h as colorless oil (21.0mg, 75% yield), 75% ee. HPLC conditions are as follows:two consecutive Daicel Chiralpak OD-3 columns (n-hexane/isopropanol 100/0, 1.0mL/min) were used, lambda 250nm, temperature 28 ℃, tr(major)＝11.4min,tr(minor)＝11.9min。
[α]D 25.8＝-27(c＝0.1,CHCl3)。
1H NMR(600MHz,CDCl3):δ＝7.72(d,J＝6.8Hz,2H),7.58(d,J＝7.7Hz,1H),7.55(d,J＝8.3Hz,1H),7.43(t,J＝7.3Hz,1H),7.39(t,J＝7.1Hz,2H),7.30(t,J＝7.7Hz,1H),7.25–7.19(m,1H),7.14(s,1H),4.73(s,1H),1.12(s,9H)ppm。
13C NMR(150MHz,CDCl3):δ＝158.4,157.5,135.7,131.9,129.9,127.9,127.6,124.7,122.5,121.1,120.1,111.5,27.0,17.6ppm。
HRMS (ESI) accurate mass calculation of C18H21OSi[M+H]+281.1356, found 281.1365.
Example 9
Compound 5 i.
Synthesized according to step C, 5i was obtained as a colorless oil (13.4mg, 52% yield) by silica gel column chromatography (petroleum ether) in 90% ee. HPLC conditions: a Daicel Chiralpak OD-H column (n-hexane/isopropanol 100/0, 0.5mL/min) was used, with a lambda of 250nm, at a temperature of 28 ℃ and tr(minor)＝10.6min,tr(major)＝12.2min。
[α]D 25.5＝-14(c＝0.1,CHCl3)。
1H NMR(400MHz,CDCl3):δ＝7.69–7.62(m,2H),7.41–7.33(m,3H),7.20(d,J＝3.3Hz,1H),6.88–6.84(m,1H),4.71(s,1H),2.54(d,J＝0.6Hz,3H),1.05(s,9H)ppm。
13C NMR(100MHz,CDCl3):δ＝146.7,137.8,135.5,133.7,129.5,129.2,127.8,126.9,27.1,17.7,15.1ppm。
HRMS (ESI) accurate massCalculating C15H21SSi[M+H]+261.1128, found 261.1129.
Example 10
Compound 5 j.
Referring to the synthesis of step C (reaction at room temperature for 48h), 5j was obtained as a white foam (19.6mg, 63% yield), 80% ee by silica gel column chromatography (petroleum ether). HPLC conditions: a Daicel Chiralpak OD-3 column (n-hexane/isopropanol 100/0, 0.6mL/min) was used, with a lambda of 250nm, at a temperature of 28 ℃ and tr(major)＝14.2min,tr(minor)＝15.6min。
[α]D 25.5＝-7(c＝0.1,CHCl3)。
1H NMR(400MHz,CDCl3):δ＝7.91–7.85(m,1H),7.84–7.79(m,1H),7.65–7.57(m,3H),7.37–7.29(m,2H),7.21(d,J＝7.6Hz,2H),4.81(s,1H),2.37(s,3H),1.11(s,9H)ppm。
13C NMR(100MHz,CDCl3):δ＝144.0,140.7,139.8,135.7,134.4,134.2,129.1,128.8,124.5,124.0,123.6,122.0,27.2,21.6,17.8ppm。
HRMS (ESI) accurate mass calculation of C19H22NaSSi[M+Na]+333.1104, found 333.1108.
Example 11
Compound 5 k.
Referring to step C synthesis, dihydrosilane substrate 1(0.1mmol), [ Rh (cod) Cl]2(4 mol%), ligand L7(R, R) -iPr-BPE (8.8 mol%), in 1.0mL benzene at 80 ℃ for 24 hours.
Silica gel column chromatography (petroleum ether) afforded 5k as a colorless oil (14.5mg, 54% yield), 45% ee. HPLC conditions: using Daicel Chiralpak IC chromatographyColumn (n-hexane/isopropanol 100/0, 0.5mL/min), λ 220nm, temperature 28 ℃, tr(minor)＝14.9min,tr(major)＝16.2min。
[α]D 24.3＝-7(c＝0.1,CHCl3)。
1H NMR(400MHz,CDCl3):δ＝7.68–7.62(m,2H),7.61–7.56(m,2H),7.41–7.32(m,3H),6.95–6.89(m,2H),4.61(s,1H),3.81(s,3H),1.05(s,9H)ppm。
13C NMR(100MHz,CDCl3):δ＝160.7,137.2,135.7,134.4,129.3,127.8,124.7,113.6,55.0,27.5,17.8ppm。
HRMS (ESI) accurate mass calculation of C17H23OSi[M+H]+271.1513, found 271.1515.
Example 12
Compound 5 l.
Referring to step C synthesis, dihydrosilane substrate 1(0.1mmol), [ Rh (cod) Cl]2(4 mol%), ligand L7(R, R) -iPr-BPE (8.8 mol%), in 1.2g naphthalene at 80 ℃ for 24 hours.
5l was obtained by silica gel column chromatography (petroleum ether) as a colorless oil (8.0mg, yield 25%) and 31% ee. HPLC conditions: a Daicel Chiralpak IC column (n-hexane/isopropanol 100/0, 0.5mL/min) was used, lambda 250nm, at 28 ℃ and tr(minor)＝27.6min,tr(major)＝30.4min。
[α]D 24.9＝-4(c＝0.1,CHCl3)。
1H NMR(400MHz,CDCl3):δ＝8.15(s,1H),7.86–7.80(m,3H),7.71(dd,J＝8.2,1.0Hz,1H),7.66–7.61(m,2H),7.53–7.45(m,2H),6.96–6.91(m,2H),4.74(s,1H),3.82(s,3H),1.10(s,9H)ppm。
13C NMR(100MHz,CDCl3):δ＝160.7,137.2,136.8,133.8,132.9,132.0,131.6,128.2,127.7,126.9,126.5,125.9,124.6,113.7,55.0,27.6,18.0ppm。
Example 13
Compound 5 m.
Referring to step C synthesis, dihydrosilane substrate 1(0.1mmol), [ Rh (cod) Cl]2(4 mol%), ligand L7(R, R) -iPr-BPE (8.8 mol%), in 1.0mL m-xylene at 80 ℃ for 24 hours.
Silica gel column chromatography (petroleum ether) afforded 5m as a colorless oil (8.0mg, 27% yield), 40% ee. HPLC conditions: a Daicel Chiralpak OD-3 column (n-hexane/isopropanol 100/0, 1.0mL/min) was used, with a lambda of 220nm, at a temperature of 28 ℃ and a temperature of tr(major)＝6.5min,tr(minor)＝7.4min。
[α]D 25.1＝+3(c＝0.1,CHCl3)。
1H NMR(400MHz,CDCl3):δ＝7.61–7.55(m,2H),7.25(s,2H),7.02(s,1H),6.94–6.88(m,2H),4.56(s,1H),3.81(s,3H),2.31(s,6H),1.05(s,9H)ppm。
13C NMR(100MHz,CDCl3):δ＝160.6,137.2,137.0,134.0,133.4,131.1,125.0,113.6,55.0,27.6,21.4,17.8ppm。
Example 14
Compound 5 n.
Referring to step C synthesis, dihydrosilane substrate 1(0.1mmol), [ Rh (cod) Cl]2(4 mol%), ligand L7(R, R) -iPr-BPE (8.8 mol%), in 1.0mL 1, 3-bis (trifluoromethyl) benzene at 80 ℃ for 24 hours.
Silica gel column chromatography (petroleum ether) afforded 5n as a colorless oil (17.8mg, 44% yield), 68% ee. HPLC conditions: using a Daicel Chiralpak OD-3 column (n-hexane/isopropanol 100/0, 1.0mL/min),λ 250nm, temperature 28 ℃, tr(major)＝4.6min,tr(minor)＝5.2min。
[α]D 25.0＝-55(c＝0.1,CHCl3)。
When using L1 as ligand, the yield of 5n was 38% and ee was 24% [ t ] compared to (R, R) -iPr-BPEr(minor)＝4.6min,tr(major)＝5.1min.)]This confirms that the configuration of 5n is reversed in the two ligands.
1H NMR(400MHz,CDCl3):δ＝8.05(s,2H),7.88(s,1H),7.55(d,J＝8.6Hz,2H),6.96(d,J＝8.6Hz,2H),4.69(s,1H),3.83(s,3H),1.07(s,9H)ppm。
13C NMR(100MHz,CDCl3):δ＝161.3,138.3,137.1,135.2,130.8(q,JC-F＝32.7Hz),123.5(q,JC-F＝271.5Hz),123.2–123.1(m),122.2,114.1,55.1,27.3,17.8ppm。19F NMR(376MHz,CDCl3):δ＝-62.84ppm。
Example 15
Compound 5 o.
Referring to step C synthesis, dihydrosilane substrate 1(0.1mmol), [ Rh (cod) Cl]2(4 mol%), ligand L7(R, R) -iPr-BPE (8.8 mol%), in 1.0mL 1, 4-difluorobenzene at 80 deg.C for 24 hours.
Column chromatography on silica gel (petroleum ether) afforded 5o as a colorless oil (9.2mg, 30% yield), 68% ee. HPLC conditions: a Daicel Chiralpak IC column (n-hexane/isopropanol 100/0, 0.5mL/min) was used, lambda 250nm, at 28 ℃ and tr(minor)＝12.2min,tr(major)＝12.9min。
[α]D 25.0＝-11(c＝0.1,CHCl3)。
1H NMR(400MHz,CDCl3):δ＝7.65–7.60(m,2H),7.23–7.17(m,1H),7.07–6.96(m,2H),6.95–6.91(m,2H),4.62(d,J＝3.5Hz,1H),3.82(s,3H),1.06(s,9H)ppm。
13C NMR(100MHz,CDCl3):δ＝162.4(dd,JC-F＝236.0,1.9Hz),161.0,158.6(dd,JC-F＝242.2,2.1Hz),137.2(d,JC-F＝2.0Hz),123.4(dd,JC-F＝26.8,16.6Hz),123.4(dd,JC-F＝22.1,11.9Hz),123.0,118.2(dd,J＝24.4,9.2Hz),116.2(dd,J＝29.7,7.8Hz),113.8,55.0,27.5(d,JC-F＝1.3Hz),18.0ppm。
19F NMR(376MHz,CDCl3):δ＝-102.97(d,J＝20.3Hz),-120.17(d,J＝20.4Hz)ppm。
HRMS (ESI) accurate mass calculation of C17H21F2OSi[M+H]+307.1324, found 307.1328.
Example 16
Compound 5 p.
Synthesized according to step C, 5p was obtained as a colorless oil (19.8mg, 60% yield) by silica gel column chromatography (petroleum ether) in 90% ee. HPLC conditions: a Daicel Chiralpak OD-3 column (n-hexane/isopropanol 100/0, 1.0mL/min) was used, with a lambda of 250nm, at a temperature of 28 ℃ and tr(major)＝3.5min,tr(minor)＝3.9min。
[α]D 25.6＝-18(c＝0.1,CHCl3)。
1H NMR(400MHz,CDCl3):δ＝7.62(d,J＝7.9Hz,2H),7.50(d,J＝7.9Hz,2H),6.57(s,1H),4.55(s,1H),2.25(s,3H),1.93(s,3H),1.05(s,9H),0.26(s,9H)ppm。
13C NMR(100MHz,CDCl3):δ＝153.0,150.3,141.8,134.8,133.5,132.5,127.3,114.1,27.1,17.5,11.8,9.7,-1.2ppm。
HRMS (ESI) accurate mass calculation of C19H31OSi2[M+H]+331.1908, found 331.1907.
Example 17
Compound 5 q.
Synthesized according to step C, 5q as a colorless oil (18.2mg, 61% yield) obtained by silica gel column chromatography (petroleum ether) in 90% ee. HPLC conditions: a Daicel Chiralpak OD-3 column (n-hexane/isopropanol 99/1, 1.0mL/min) was used, with a lambda of 250nm, at a temperature of 28 ℃ and tr(minor)＝4.9min,tr(major)＝5.3min。
[α]D 25.2＝-7(c＝0.1,CHCl3)。
1H NMR(400MHz,CDCl3):δ＝7.46(d,J＝0.6Hz,1H),7.39(dd,J＝7.9,1.2Hz,1H),6.80(d,J＝7.9Hz,1H),6.55(s,1H),4.56(t,J＝8.7Hz,2H),4.52(s,1H),3.21(t,J＝8.7Hz,2H),2.25(s,3H),1.93(s,3H),1.03(s,9H)ppm。
13C NMR(100MHz,CDCl3):δ＝161.5,152.9,150.8,135.9,132.1,127.1,126.6,123.5,114.1,109.2,71.1,29.5,27.0,17.5,11.8,9.7ppm。
HRMS (ESI) accurate mass calculation of C18H25O2Si[M+H]+301.1618, found 301.1618.
Example 18
Compound 5 r.
Synthesized according to step C, 5r was obtained as a colorless oil (16.6mg, 60% yield), 88% ee by silica gel column chromatography (petroleum ether). HPLC conditions: a Daicel Chiralpak OD-H column (n-hexane/isopropanol 100/0, 0.5mL/min) was used, with a lambda of 250nm, at a temperature of 28 ℃ and tr(major)＝7.9min,tr(minor)＝8.1min。
[α]D 25.4＝-13(c＝0.1,CHCl3)。
1H NMR(400MHz,CDCl3):δ＝7.66–7.59(m,2H),7.06(t,J＝8.9Hz,2H),6.57(s,1H),4.55(s,1H),2.25(s,3H),1.94(s,3H),1.03(s,9H)ppm。
13C NMR(100MHz,CDCl3):δ＝164.1(d,JC-F＝247.1Hz),153.2,149.9,137.6(d,JC-F＝7.5Hz),128.6(d,JC-F＝4.0Hz),127.4,115.0(d,JC-F＝19.6Hz),114.2,26.9,17.4,11.8,9.7ppm。
19F NMR(376MHz,CDCl3) D-111.12 ppm hrms (ESI) accurate mass calculation of C16H22FOSi[M+H]+277.1418, found 277.1419.
Example 19
Compound 5 s.
Synthesized according to step C, obtained by silica gel column chromatography (petroleum ether) for 5s as a colorless oil (20.6mg, 67% yield), 90% ee. HPLC conditions are as follows: a Daicel Chiralpak OD-3 column (n-hexane/isopropanol 100/0, 1.0mL/min) was used, with a lambda of 250nm, at a temperature of 28 ℃ and tr(major)＝6.6min,tr(minor)＝7.8min。
[α]D 25.4＝-18(c＝0.1,CHCl3)。
1H NMR(400MHz,CDCl3):δ＝8.16(s,1H),7.86–7.80(m,3H),7.71(dd,J＝8.2,0.9Hz,1H),7.52–7.45(m,2H),6.61(s,1H),4.70(s,1H),2.27(s,3H),1.94(s,3H),1.08(s,9H)ppm。
13C NMR(100MHz,CDCl3):δ＝153.2,150.2,136.8,133.9,132.9,131.5,130.7,128.2,127.7,127.5,126.9,126.5,125.9,114.2,27.1,17.7,11.8,9.7ppm。
HRMS (ESI) accurate mass calculation of C20H25OSi[M+H]+309.1669, found 309.1669.
Example 20
Compound 5 t.
Synthesized according to step C, 5t was obtained as a white solid (18.4mg, 52% yield) by silica gel column chromatography (petroleum ether) in 80% ee. HPLC conditions: a Daicel Chiralpak IC column (n-hexane/isopropanol 95/5, 0.5mL/min) was used, lambda 250nm, at 28 ℃ and tr(minor)＝7.0min,tr(major)＝7.5min。
[α]D 25.1＝-12(c＝0.1,CHCl3)。
1H NMR(400MHz,CDCl3):δ＝8.52(d,J＝9.2Hz,1H),8.37(d,J＝7.6Hz,1H),8.22–8.14(m,3H),8.13–7.98(m,4H),7.82(d,J＝1.3Hz,1H),6.92(d,J＝3.2Hz,1H),6.47(dd,J＝3.2,1.6Hz,1H),5.38(s,1H),1.15(s,9H)ppm。
13C NMR(100MHz,CDCl3):δ＝154.2,147.7,136.5,134.6,132.6,131.2,130.7,128.6,128.3,128.1,127.5,127.4,125.9,125.3,124.7,124.6,124.0,124.0,109.7,27.7,18.7ppm。
HRMS (ESI) accurate mass calculation of C24H23OSi[M+H]+355.1513, found 355.1513.
The absolute configuration of compound 5t was determined by X-ray crystallography.
Compound 5t was precipitated from a culture system of methylene chloride and n-hexane, and the X-ray crystal structure data was stored in Cambridge crystallography data center under the number CCDC 2098352. Diffraction data were collected on a Bruker D8 venture using Cu-K.alpha.diffraction
The crystal structure is shown in FIG. 1, and the detailed information is shown in the following table.
Example 21
Compound 5 v.
Synthesized according to step C, 5v obtained as a colorless oil (8.8mg, 30% yield) by silica gel column chromatography (petroleum ether) in 55% ee. HPLC conditions: a Daicel Chiralpak OD-3 column (n-hexane/isopropanol 100/0, 1.0mL/min) was used, with a lambda of 250nm, at a temperature of 28 ℃ and tr(major)＝13.2min,tr(minor)＝14.5min。
[α]D 24.9＝-9(c＝0.1,CHCl3)。
1H NMR(400MHz,CDCl3):δ＝7.65(dd,J＝7.7,1.4Hz,2H),7.47–7.34(m,4H),7.04(s,1H),7.02(d,J＝2.5Hz,1H),6.91(dd,J＝8.9,2.6Hz,1H),4.78(d,J＝3.0Hz,1H),3.83(s,3H),1.54–1.45(m,1H),1.20–1.12(m,6H)ppm。
13C NMR(100MHz,CDCl3):δ＝158.4,155.8,153.7,135.4,131.8,130.0,128.2,128.0,119.9,113.9,111.8,103.1,55.9,18.2,18.1,11.7ppm。
HRMS (ESI) accurate mass calculation of C18H21O2Si[M+H]+297.1305, found 297.1305.
Example 22
Compound 5 w.
Synthesized according to step C, 5w as colorless oil (11.8mg, 35% yield), 54% ee was obtained by silica gel column chromatography (petroleum ether). HPLC conditions: a Daicel Chiralpak OD-3 column (n-hexane/isopropanol 100/0, 1.0mL/min) was used, with a lambda of 250nm, at a temperature of 28 ℃ and tr(minor)＝15.1min,tr(major)＝16.0min。
[α]D 24.9＝-31(c＝0.1,CHCl3)。
1H NMR(400MHz,CDCl3):δ＝7.64(dd,J＝7.8,1.6Hz,2H),7.45–7.34(m,4H),7.04–7.01(m,2H),6.91(dd,J＝8.9,2.6Hz,1H),4.76(d,J＝1.6Hz,1H),3.83(s,3H),1.93–1.79(m,2H),1.77–1.65(m,3H),1.36–1.31(m,3H),1.28–1.20(m,3H)ppm。
13C NMR(100MHz,CDCl3):δ＝158.5,155.8,153.7,135.4,131.8,129.9,128.2,128.0,119.8,113.8,111.8,103.1,55.9,28.0,28.0,27.7,26.6,23.3ppm。
HRMS (ESI) accurate mass calculation of C21H25O2Si[M+H]+337.1618, found 337.1620.
Example 23
Compound 5 x.
Synthesis according to step C, using [ Rh (cod) Cl]2(4 mol%), L4(8.8 mol%). Obtained by silica gel column chromatography (petroleum ether) 5x as a white solid (25.8mg, 72% yield), 40% ee. HPLC conditions: a Daicel Chiralpak AD-3 column (n-hexane/isopropanol 99/1, 0.5mL/min) was used, with a lambda of 250nm, at a temperature of 28 ℃ and tr(major)＝9.5min,tr(minor)＝10.4min。
[α]D 22.4＝+42(c＝0.1,CHCl3)。
1H NMR(400MHz,CDCl3):δ＝7.63(d,J＝6.7Hz,2H),7.46–7.34(m,4H),7.29–7.23(m,1H),7.09–7.00(m,4H),6.92(dd,J＝8.9,2.4Hz,1H),5.83(s,1H),3.83(s,3H),2.40(s,6H)ppm。
13C NMR(100MHz,CDCl3):δ＝158.3,155.8,153.8,145.7,135.3,131.9,130.5,130.0,128.8,128.3,128.2,127.9,120.5,114.0,111.9,103.1,55.9,24.3ppm。
HRMS (ESI) accurate mass calculation of C23H23O2Si[M+H]+359.1462, found 359.1462.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A silicon-centered chiral aryl silane having the structure of formula i:
wherein R is1Selected from alkyl, cycloalkyl, 2, 6-dimethylphenyl;
R2is selected from phenyl, naphthyl, pyrenyl, 2, 3-dihydrobenzofuranyl, or phenyl substituted by alkyl, alkoxy, halogen and trialkylsilyl;
ar is selected from phenyl, naphthyl, furyl, 2-methylthiophene, benzofuryl, benzothienyl, 5-methoxybenzofuran, alkyl, benzyl, trimethylsilyl, thioether, phenyl-substituted furyl, alkyl, trifluoromethyl, halogen-substituted phenyl.
2. The silicon-centered chiral aryl silane of claim 1, wherein R is1Selected from (C1-C4) alkyl, (C5-C7) cycloalkyl and 2, 6-dimethylphenyl.
3. The silicon-centered chiral aryl silane of claim 2, wherein R is1Selected from tert-butyl, isopropyl, cyclohexyl and 2, 6-dimethylphenyl.
4. The silicon-centered chiral heteroarylsilane of claim 1, whereinIn that R is2Is selected from phenyl, naphthyl, pyrenyl, 2, 3-dihydrobenzofuranyl, or phenyl substituted by methyl, methoxy, fluorine and trimethylsilyl.
5. The silicon-centered chiral aryl silane of claim 1, wherein Ar is selected from phenyl, naphthyl, furyl, 2-methylthiophenyl, benzofuryl, benzothienyl, 5-methoxybenzofuranyl, or (C1-C4) alkyl, benzyl, trimethylsilyl, iPrSCH2Phenyl substituted furyl or (C1-C4) alkyl, trifluoromethyl, halogen substituted phenyl.
6. The silicon-centered chiral arylsilane of claim 5 wherein Ar is selected from phenyl, 2-naphthyl, and one of the following substituents:
7. the silicon-centered chiral heteroarylsilane according to claim 1, which is selected from one of the following compounds:
8. a method for preparing a silicon-centered chiral heteroaryl silane as claimed in any one of claims 1 to 7, comprising the steps of: in the presence of a chiral ligand and a rhodium catalyst, the compound of formula 1 and the compound of formula 2 are reacted as follows
The rhodium catalyst is [ Rh (cod) Cl]2、[Rh(cod)OH]2、[Rh(nbd)Cl]2Or [ Rh (CO) ]2Cl]2；
The chiral ligand is selected from the following compounds:
r, R' are each independently selected from the group consisting of tert-butyl, cyclohexyl, phenyl, 2-methylphenyl, 4-trifluoromethylphenyl, 3, 5-dimethylphenyl, 3, 5-dimethyl-4-methoxyphenyl, 3, 5-di-tert-butyl-4-methoxyphenyl;
R1、R2ar is as defined in claims 1 to 6.
9. The process according to claim 8, wherein the chiral ligand is selected from the group consisting of:
10. the process according to claim 8 or 9, wherein the reaction is carried out by adding cyclohexene, NBE or NBE-OMe as a hydrogen acceptor; the dosage of the chiral ligand is at least 3 mol%, the dosage of the rhodium catalyst is at least 1 mol%, and the dosage of the hydrogen acceptor is at least 100 mol%; the molar ratio of the compound shown in the formula 1 to the compound shown in the formula 2 is (1-3): 1; the reaction takes toluene, benzene, naphthalene, m-xylene, 1, 3-bis (trifluoromethyl) benzene or 1, 4-difluorobenzene as a solvent; the reaction temperature is above 20 ℃, and the reaction time is at least 24 h.
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| CN115010743A (en) * | 2022-06-21 | 2022-09-06 | 深圳湾实验室 | Preparation method of monohydrosilanes compound |
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| CN115010743A (en) * | 2022-06-21 | 2022-09-06 | 深圳湾实验室 | Preparation method of monohydrosilanes compound |
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