CN102746343A - Chiral bis-imidazoline pincer rhodium compound, preparation and asymmetric catalysis application thereof - Google Patents
Chiral bis-imidazoline pincer rhodium compound, preparation and asymmetric catalysis application thereof Download PDFInfo
- Publication number
- CN102746343A CN102746343A CN201210271081XA CN201210271081A CN102746343A CN 102746343 A CN102746343 A CN 102746343A CN 201210271081X A CN201210271081X A CN 201210271081XA CN 201210271081 A CN201210271081 A CN 201210271081A CN 102746343 A CN102746343 A CN 102746343A
- Authority
- CN
- China
- Prior art keywords
- imidazoline
- chirality
- carbon
- compound
- pincerlike
- 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.)
- Granted
Links
- 150000003284 rhodium compounds Chemical class 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 210000000080 chela (arthropods) Anatomy 0.000 title claims abstract description 4
- 238000006555 catalytic reaction Methods 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- FHUDAMLDXFJHJE-UHFFFAOYSA-N 1,1,1-trifluoropropan-2-one Chemical compound CC(=O)C(F)(F)F FHUDAMLDXFJHJE-UHFFFAOYSA-N 0.000 claims abstract description 36
- -1 trifluoromethyl propargyl tertiary alcohol Chemical class 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 15
- 150000001345 alkine derivatives Chemical group 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 69
- DZPXBTZJEFYBBK-UHFFFAOYSA-N 1-(4,5-dihydroimidazol-1-yl)-4,5-dihydroimidazole Chemical compound C1=NCCN1N1C=NCC1 DZPXBTZJEFYBBK-UHFFFAOYSA-N 0.000 claims description 61
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 229910052799 carbon Inorganic materials 0.000 claims description 32
- 238000004809 thin layer chromatography Methods 0.000 claims description 32
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 31
- 229910052786 argon Inorganic materials 0.000 claims description 27
- 239000002585 base Substances 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 125000001424 substituent group Chemical group 0.000 claims description 18
- 150000003509 tertiary alcohols Chemical class 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- 230000003287 optical effect Effects 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Chemical group 0.000 claims description 4
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Chemical group 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000005504 styryl group Chemical group 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 125000001544 thienyl group Chemical group 0.000 claims description 4
- HSSMNYDDDSNUKH-UHFFFAOYSA-K trichlororhodium;hydrate Chemical compound O.Cl[Rh](Cl)Cl HSSMNYDDDSNUKH-UHFFFAOYSA-K 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 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 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- LJWKFGGDMBPPAZ-UHFFFAOYSA-N ethoxyethane;toluene Chemical compound CCOCC.CC1=CC=CC=C1 LJWKFGGDMBPPAZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Chemical group 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims 4
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims 1
- 238000005905 alkynylation reaction Methods 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000007294 asymmetric addition reaction Methods 0.000 abstract 1
- KJHQVUNUOIEYSV-UHFFFAOYSA-N ethyl 3,3,3-trifluoro-2-oxopropanoate Chemical compound CCOC(=O)C(=O)C(F)(F)F KJHQVUNUOIEYSV-UHFFFAOYSA-N 0.000 abstract 1
- 239000012141 concentrate Substances 0.000 description 30
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 23
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 230000002194 synthesizing effect Effects 0.000 description 8
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 7
- HNJJXZKZRAWDPF-UHFFFAOYSA-N methapyrilene Chemical compound C=1C=CC=NC=1N(CCN(C)C)CC1=CC=CS1 HNJJXZKZRAWDPF-UHFFFAOYSA-N 0.000 description 7
- 239000012300 argon atmosphere Substances 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 5
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WLFTZMAAXHUNDE-UHFFFAOYSA-N 1,1,1,7,7,7-hexafluoroheptan-4-one Chemical compound FC(F)(F)CCC(=O)CCC(F)(F)F WLFTZMAAXHUNDE-UHFFFAOYSA-N 0.000 description 2
- XPOQHMRABVBWPR-UHFFFAOYSA-N Efavirenz Natural products O1C(=O)NC2=CC=C(Cl)C=C2C1(C(F)(F)F)C#CC1CC1 XPOQHMRABVBWPR-UHFFFAOYSA-N 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 229940125773 compound 10 Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- XPOQHMRABVBWPR-ZDUSSCGKSA-N efavirenz Chemical compound C([C@]1(C2=CC(Cl)=CC=C2NC(=O)O1)C(F)(F)F)#CC1CC1 XPOQHMRABVBWPR-ZDUSSCGKSA-N 0.000 description 2
- 229960003804 efavirenz Drugs 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- DKFHWNGVMWFBJE-UHFFFAOYSA-N 1-ethynylcyclohexene Chemical group C#CC1=CCCCC1 DKFHWNGVMWFBJE-UHFFFAOYSA-N 0.000 description 1
- 208000030507 AIDS Diseases 0.000 description 1
- YLIAWYPQYFNYRS-UHFFFAOYSA-N C#C.C1=CC=CC2=CC=CC=C21 Chemical group C#C.C1=CC=CC2=CC=CC=C21 YLIAWYPQYFNYRS-UHFFFAOYSA-N 0.000 description 1
- 0 CC1C(C)=CC(C#CC(*)(C(F)(F)F)O)=CC1 Chemical compound CC1C(C)=CC(C#CC(*)(C(F)(F)F)O)=CC1 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CRFJRGSTIQFTQW-UHFFFAOYSA-N acetylene fluorobenzene Chemical group C#C.FC1=CC=CC=C1 CRFJRGSTIQFTQW-UHFFFAOYSA-N 0.000 description 1
- BLJLOSJXZCESDI-UHFFFAOYSA-N acetylene toluene Chemical group C#C.CC1=CC=CC=C1 BLJLOSJXZCESDI-UHFFFAOYSA-N 0.000 description 1
- QDJZBFLFHUMZBE-UHFFFAOYSA-N acetylene;bromobenzene Chemical group C#C.BrC1=CC=CC=C1 QDJZBFLFHUMZBE-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000012773 agricultural material Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000000078 anti-malarial effect Effects 0.000 description 1
- 239000003430 antimalarial agent Substances 0.000 description 1
- BJDCWCLMFKKGEE-ISOSDAIHSA-N artenimol Chemical compound C([C@](OO1)(C)O2)C[C@H]3[C@H](C)CC[C@@H]4[C@@]31[C@@H]2O[C@H](O)[C@@H]4C BJDCWCLMFKKGEE-ISOSDAIHSA-N 0.000 description 1
- 229960002521 artenimol Drugs 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229930016266 dihydroartemisinin Natural products 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a chiral bis-imidazoline pincer rhodium compound and an asymmetric addition reaction method of ethyl trifluoropyruvate with terminal alkyne under the catalysis of the compound. Optically active trifluoromethyl propargyl tertiary alcohol is synthesized in a high enantioselectivity mode. The rhodium compound is simple in preparation, easy to modify in structure and good in stability. During an asymmetric alkynylation reaction for catalyzing the trifluoroacetone acid, the catalyst dosage is few, the reaction temperature is mild and controllable, the application range of a substrate is wide, and the product- optically active trifluoromethyl propargyl tertiary alcohol has a high yield and an enantio-selectivity higher than 95% in most instances.
Description
Technical field
The invention belongs to metal-organic synthetic and applied technical field; Relate to the preparation of the pincerlike rhodium compound of one type of chirality bi-imidazoline and under such compound for catalysis; Trifluoroacetone acid esters and end-group alkyne carry out asymmetric reduction reaction, and high enantioselectivity ground has synthesized optically active trifluoromethyl alkynes third tertiary alcohol.
Background technology
Optically active propargyl tertiary alcohol is the important intermediate of multiple medicine and natural product; It also is synthetic building block very useful in the organic synthesis; In chiral catalyst (generally including metal and chiral ligand) effect down, the asymmetric alkynylation reaction of prochiral ketones be synthesize this compounds the most directly, one of effective means.Yet because the reactive behavior of ketone is relatively low, the example of asymmetric alkynylation reaction is also fewer.In the alkynylation reaction of having reported; In most cases, need to use excessive organometallic reagent as: proton, original position that organolithium, Grignard reagent or dialkyl group zinc are sloughed end-group alkyne generate the nucleophilic reagent of the alkynyl metal reagent of metering as attack ketone; Sometimes the use of chiral ligand is also measured.And consider that from Atom economy the consumption of metal reagent and chiral ligand is catalytic amount preferably, the asymmetric alkynylation reaction of the catalysis of development of high efficient, ketone is extremely important.Wherein, It is then especially noticeable that trifluorumethylketones etc. contain the asymmetric alkynylization of carbonyl compound of trifluoromethyl; Because the optical activity tertiary alcohol that contains trifluoromethyl that obtains is the key intermediate of bioactive moleculess such as some medicines; For example: the asymmetric addition of trifluorumethylketone and alkynyl metal reagent is used to synthetic Efavirenz, and Efavirenz and analogue thereof are effective non-nuclear former times class RTIs, be widely used in clinically treating AIDS (
J. Am. Chem. Soc.,
1998,
120, 2028;
Angew. Chem. Int. Ed.,
1999,
38, 711;
J. Med. Chem.
2000,
43, 2019.); In fact, this addition reaction also is the reported first of the asymmetric alkynylation reaction of ketone.In addition; Also there are some researches show; In organic molecule, introduce physico-chemical property and the biological property that trifluoromethyl can change parent compound; For example introduce trifluoromethyl at the C-10 place of Dihydroartemisinin and verivate thereof, not only the chemicalstability of compound obviously strengthens and also antimalarial active also improve greatly (
J. Med. Chem. 2004,
47, 2694.); And the optical activity organic cpds that contains trifluoromethyl also has important use in fields such as agricultural chemicals and materials, therefore, how to make up these compounds efficiently and be a problem that is worth very much research (
Chem. Rev. 2011,
111, 455.).
The same with trifluorumethylketone, the trifluoroacetone acid esters also is the carbonyl compound that contains trifluoromethyl commercial, that be easy to get, and the catalystsystem that is successfully used to trifluoroacetone acid esters alkynylation reaction only have three examples (comprise a routine achirality, be respectively:
Synlett.
2008,
10, 1571;
Org. Lett. 2010,
12, 5716;
Angew. Chem. Int. Ed.
2011,
50, 6296).
Summary of the invention
Pincerlike metallic compound has characteristics such as stability is higher, the easy modification of structure, has been successfully used to the polytype reaction of catalysis.However, the report that the pincerlike metallic compound of chirality and asymmetry catalysis thereof are used is also less relatively, and the example that especially stereoselectivity is high is actually rare.For the kind that increases this compounds and open up its Application Areas, the purpose of this invention is to provide the pincerlike rhodium compound of bi-imidazoline and the preparation method of chirality.
Another object of the present invention provides the pincerlike rhodium compound of a kind of use chirality bi-imidazoline as catalyzer, carries out asymmetric reduction reaction by trifluoroacetone acid esters and end-group alkyne, the method for high enantioselectivity ground synthesis of optically active trifluoromethyl alkynes third tertiary alcohol.As one type of chiral catalyst, above-mentioned chirality rhodium compound preparation is simple, structure is prone to modify, and good stability; Consumption is few when being used for catalyzed reaction, and reaction conditions is gentle to be prone to control, substrate applied widely, and the yield of products therefrom-optical activity trifluoromethyl alkynes third tertiary alcohol is high, in most of the cases enantio-selectivity is greater than 95%.
The present invention adopts following technical scheme to realize above-mentioned purpose:
The pincerlike rhodium compound of one type of chirality bi-imidazoline is characterized in that: for the compound shown in the following formula (I):
Formula (I)
R is hydrogen, nitro or halogen in the formula (I); R
1Be hydrogen, benzyl, optional alkyl or optional aryl with substituent 6-12 carbon with substituent 1-6 carbon; R
2Be hydrogen or optional aryl with substituent 6-12 carbon; R
3For choosing the alkyl with substituent 1-6 carbon, optional naphthenic base or optional aryl wantonly with substituent 6-12 carbon with substituent 3-6 carbon; X is cl ions or acetate ion, and the substituting group on abovementioned alkyl, naphthenic base or the aryl is the alkyl of 1-6 carbon, the naphthenic base of 3-6 carbon or the aryl of 6-12 carbon.
Described optional alkyl preferable methyl, sec.-propyl, the tertiary butyl, sec.-butyl or isobutyl-with substituent 1-6 carbon, described optional preferred cyclopentyl of naphthenic base or cyclohexyl with substituent 3-6 carbon; The described optional preferred phenyl of aryl with substituent 6-12 carbon, p-methylphenyl, p-methoxyphenyl, to ethoxyl phenenyl, 2,6-diisopropyl phenyl or right-chloro-phenyl-.
The compound method of the pincerlike rhodium compound of chirality bi-imidazoline; Its synthesis step: with bi-imidazoline base benzene-like compounds between chirality; With three rhodium trichloride hydrate reacting by heating, solvent evaporated, thin-layer chromatography separation and purification promptly get the chirality bi-imidazoline pincer rhodium compound of the formula that X is a cl ions (I) then in solvent, in the presence of the alkali; Then add Silver monoacetate solution, stirring at room, filtering and concentrating promptly get the pincerlike rhodium compound of chirality bi-imidazoline of the formula that X is an acetate ion (I).
Bi-imidazoline base benzene-like compounds does between described chirality
, wherein R, R
1, R
2, R
3Definition like above-mentioned formula (I) compound.
The mole dosage of bi-imidazoline base benzene-like compounds, alkali is 1 ~ 1.5 times of three rhodium trichloride hydrate mole dosage between described chirality; Solvent is that (volume ratio is 10 ~ 20:1) for ethanol, methyl alcohol or methanol-water mixed solvent; Alkali is triethylamine or sodium hydrogencarbonate; Heating temperature is 60 ~ 80
oC; Be 12 ~ 48 h heat-up time.
Methylene dichloride or chloroformic solution that described Silver monoacetate solution is Silver monoacetate; The mole dosage of Silver monoacetate is 2 ~ 5 times of said rhodium compound (X is a cl ions); The stirring at room time is 24 ~ 48 h.
The pincerlike rhodium compound of above-mentioned chirality bi-imidazoline is in the asymmetric reduction reaction of catalysis trifluoroacetone acid esters and end-group alkyne, the application in synthesis of optically active trifluoromethyl alkynes third tertiary alcohol.
The synthetic employing following steps of optical activity trifluoromethyl alkynes third tertiary alcohol: chirality rhodium compound catalyzer, trifluoroacetone acid esters and end-group alkyne are joined in the organic solvent; Concentrated and purified optical activity trifluoromethyl alkynes third tertiary alcohol that promptly gets that finishes is reacted in reaction under argon shield.
The structure of described trifluoroacetone acid esters is:
Wherein, R
4Be methyl or ethyl; The structure of described end-group alkyne does
, wherein, R
5Naphthenic base, cyclohexenyl, naphthyl, thienyl or R for the alkyl of 1-6 carbon, styroyl, styryl, 3-6 carbon
6Substituted phenyl, described R
6Substituted phenyl, R
6Be hydrogen, methyl, ethyl, the tertiary butyl, methoxyl group, fluorine, chlorine, bromine, trifluoromethyl, nitro or aldehyde radical, R
6The position of substitution on phenyl ring is ortho position, a position or contraposition.
The mole dosage ratio that feeds intake of described rhodium catalyst, end-group alkyne and trifluoroacetone acid esters is 0.01 ~ 0.05:1.2 ~ 3.0:1.0; Described organic solvent is the mixed solvent of methylene dichloride, THF, ether, Di Iso Propyl Ether, toluene or toluene-ether; Temperature of reaction is 10 ~ 70
oC; Reaction times is 24 ~ 48 h.
The structure of described optical activity trifluoromethyl alkynes third tertiary alcohol is:
Wherein, R
4Be methyl or ethyl; R
5Naphthenic base, cyclohexenyl, naphthyl, thienyl or R for the alkyl of 1-6 carbon, styroyl, styryl, 3-6 carbon
6Substituted phenyl, described R
6Substituted phenyl, R
6Be hydrogen, methyl, ethyl, the tertiary butyl, methoxyl group, fluorine, chlorine, bromine, trifluoromethyl, nitro or aldehyde radical, R
6The position of substitution on phenyl ring is ortho position, a position or contraposition.
Positively effect of the present invention is:
The present invention utilizes the C2 position C-H key activation method of associated ligands; Provide one type of chirality bi-imidazoline pincerlike rhodium compound; And use it for the asymmetric reduction reaction of catalysis trifluoroacetone acid esters and end-group alkyne, realized the efficient synthetic of optical activity trifluoromethyl alkynes third tertiary alcohol.As one type of chiral catalyst, above-mentioned chirality rhodium compound has that preparation is simple, structure is prone to modify,, storage insensitive to air and moisture and advantage such as easy and simple to handle; Consumption is few when being used for catalyzed reaction, and reaction conditions is gentle to be prone to control, substrate applied widely, and also the yield of products therefrom-optical activity trifluoromethyl alkynes third tertiary alcohol is high, in most of the cases enantio-selectivity is greater than 95%.
Embodiment
Further describe the present invention below in conjunction with instance, help further to understand the present invention through following embodiment, but do not limit the scope of the invention.
Reference literature (
Tetrahedron Lett. 2006,
47, 5033) described method prepare chirality between bi-imidazoline base benzene-like compounds.
The pincerlike rhodium compound of institute's synthetic chirality bi-imidazoline has following structure in following embodiment:
Embodiment one:
The preparation of the pincerlike rhodium compound 1 of chirality bi-imidazoline:Will (
S)-1, two (4-phenyl-4,5-dihydro-1-p-methylphenyl-1H-imidazoles-2-yl)-benzene (273 mg, 0.50 mmol) of 3-, RhCl
33H
2O (131 mg, 0.50 mmol) and sodium hydrogencarbonate (42 mg, 0.50 mmol) join in the 50 mL there-necked flasks, add methyl alcohol (10 mL) and water (2 mL) then, under argon atmosphere in 60
oC stirring reaction 12 h.Stopped reaction is cooled to room temperature, concentrates, and the thin-layer chromatography separation promptly gets compound
1, productive rate 57%.The experimental data of this compound: M.p.:199-202
oC. [α]
D 20=+912 (
c0.176, CHCl
3). IR (KBr):
ν3422,3177,3029,2921,2857,1577,1490,1404,1254,1159,1106,1038,1022,823,762,699,522 cm
-1.
1H NMR (400 MHz, CDCl
3): δ 7.58 (d,
J=7.1 Hz, 4H, ArH), 7.36 (t,
J=7.3 Hz, 4H, ArH), 7.32-7.22 (m, 10H, ArH), 6.73-6.65 (m, 3H, ArH), 5.35 (app t,
J=11.5 Hz, 2H, NCH), 4.49 (app t,
J=10.2 Hz, 2H, NC
HH), 3.83 (dd,
J=9.6,12.3 Hz, 2H, NCH
H), 2.41 (s, 6H, CH
3), 1.97 (br s, 2H, OH
2).
Embodiment two:
The preparation of the pincerlike rhodium compound 2 of chirality bi-imidazoline:Will (
S)-1, two (4-benzyl-4,5-dihydro-1-p-methylphenyl-1H-imidazoles-2-yl)-benzene (345 mg, 0.60 mmol) of 3-, RhCl
33H
2O (131 mg, 0.50 mmol) and sodium hydrogencarbonate (46 mg, 0.55 mmol) join in the 50 mL there-necked flasks, add ethanol (10 mL) then, under argon atmosphere in 80
oC stirring reaction 20 h.Stopped reaction is cooled to room temperature, concentrates, and the thin-layer chromatography separation promptly gets compound
2, productive rate 52%.The experimental data of this compound: M.p.:228-230
oC. [α]
D 20=+369 (
c0.170, CHCl
3). IR (KBr):
ν3415,2923,1757,1580,1512,1405,1300,1158,1095,817,702,466 cm
-1.
1H NMR (400 MHz, CDCl
3): δ 7.31-7.26 (m, 7H, ArH), 7.23-7.17 (m, 7H, ArH), 7.11 (d,
J=8.3 Hz, 4H, ArH), 6.69-6.63 (m, 3H, ArH), 4.71-4.63 (m, 2H, NCH), 4.07 (app t,
J=10.0 Hz, 2H, NC
HH), 3.81 (dd,
J=7.2,9.7 Hz, 2H, NCH
H), 3.72 (dd,
J=3.8,14.0 Hz, 2H, CH
2Ph), 2.91 (dd,
J=10.5,14.0 Hz, 2H, CH
2Ph), 2.81 (br s, 2H, OH
2), 2.38 (s, 6H, CH
3).
Embodiment three:
Synthesizing of the pincerlike rhodium compound 3 of chirality bi-imidazoline:Will (
S,
S)-1, two (4,5-phenylbenzene-4,5-dihydro-1-cyclohexyl-1H-imidazoles-2-yl)-benzene (409 mg, 0.60 mmol) of 3-, RhCl
33H
2O (131 mg, 0.50 mmol) and sodium hydrogencarbonate (46 mg, 0.55 mmol) join in the 50 mL there-necked flasks, add methyl alcohol (10 mL) and water (2 mL) then, under argon atmosphere in 60
oC stirring reaction 24 h.Stopped reaction is cooled to room temperature, concentrates, and the thin-layer chromatography separation promptly gets compound
3, productive rate 26%.The experimental data of this compound: M.p.:221-223
oC. [α]
D 20=+432 (
c0.116, CHCl
3). IR (KBr):
ν3421,3193,2929,2854,1704,1569,1531,1486,1403,1270,1094,756,700,475 cm
-1.
1H NMR (400 MHz, CDCl
3): δ 7.82 (d,
J=8.0 Hz, 2H, ArH), 7.36-7.24 (m, 21H, ArH), 4.84 (d,
J=8.4 Hz, 2H, NCH), 4.75 (d,
J=8.4 Hz, 2H, NCH), 4.48-4.41 (m, 2H, NCy-H), 2.00-1.74 (m, 4H, CyH), 1.68-1.53 (m, 4H, CyH), 1.44-1.23 (m, 6H, CyH), 0.98-0.87 (m, 6H, CyH).
Embodiment four:
Synthesizing of the pincerlike rhodium compound 4 of chirality bi-imidazoline:Will (
S,
S)-1, two (4,5-phenylbenzene-4,5-dihydro-1-p-methylphenyl-1H-imidazoles-2-yl)-benzene (419 mg, 0.60 mmol) of 3-, RhCl
33H
2O (131 mg, 0.50 mmol) and sodium hydrogencarbonate (46 mg, 0.55 mmol) join in the 50 mL there-necked flasks, add methyl alcohol (10 mL) and water (1 mL) then, under argon atmosphere in 60
oC stirring reaction 18 h.Stopped reaction is cooled to room temperature, concentrates, and the thin-layer chromatography separation promptly gets compound
4, productive rate 34%.The experimental data of this compound: M.p.:216-218
oC. [α]
D 20=+646 (
c0.118, CHCl
3). IR (KBr):
ν3420,3167,1701,1576,1483,1403,1158,1103,751,698 cm
-1.
1H NMR (400 MHz, CDCl
3): δ 7.41 (d,
J=6.9 Hz, 4H, ArH), 7.36-7.24 (m, 18H, ArH), 7.13-7.06 (m, 5H, ArH), 6.75 (br s, 1H, ArH), 6.70-6.66 (m, 1H, ArH), 6.59 (d,
J=8.0 Hz, 2H, ArH), 5.25 (d,
J=10.0 Hz, 2H, NCH), 4.76 (d,
J=10.1 Hz, 2H, NCH), 2.32 (s, 6H, CH
3).
Embodiment five:
Synthesizing of the pincerlike rhodium compound 5 of chirality bi-imidazoline:Will (
S,
S)-5-nitro-1, two (4,5-phenylbenzene-4,5-dihydro-1-p-methylphenyl-1H-imidazoles-2-yl)-benzene (557 mg, 0.75 mmol) of 3-, RhCl
33H
2O (131 mg, 0.50 mmol) and triethylamine (76 mg, 0.75 mmol) join in the 50 mL there-necked flasks, add methyl alcohol (10 mL) then, under argon atmosphere in 60
oC stirring reaction 48 h.Stopped reaction is cooled to room temperature, concentrates, and the thin-layer chromatography separation promptly gets compound
5, productive rate 31%.The experimental data of this compound: M.p.:255-257
oC. [α]
D 20=+678 (
c0.134, CHCl
3). IR (KBr):
ν3423,3168,1698,1590,1513,1486,1452,1398,1329,1271,1106,746,699,471 cm
-1.
1H NMR (400 MHz, CDCl
3): δ 7.40-7.38 (m, 6H, ArH), 7.34-7.25 (m, 17H, ArH), 7.21-7.13 (m, 5H, ArH), 6.82 (br s, 2H, ArH), 5.26 (d,
J=11.8 Hz, 2H, NCH), 4.86 (d,
J=10.7 Hz, 2H, NCH), 2.35 (s, 6H, CH
3).
Embodiment six:
Synthesizing of the pincerlike rhodium compound 6 of chirality bi-imidazoline:With compound
1(147 mg, 0.20 mmol) joins in the 5 mL dichloromethane solutions, adds AgOAc (67 mg, 0.40 mmol) stirring at room 24 h then.Stopped reaction, filtering and concentrating promptly gets compound
6, productive rate 95%.The experimental data of this compound: M.p.:154-156
oC. [α]
D 20=+325 (
c0.156, CHCl
3). IR (KBr):
ν3416,3168,1757,1626,1578,1514,1400,1321,1158,1104,696,476 cm
-1.
1H NMR (400 MHz, CDCl
3): δ 7.43-7.41 (m, 4H, ArH), 7.31-7.22 (m, 14H, ArH), 6.72 (s, 3H, ArH), 5.39 (dd,
J=8.6,11.1 Hz, 2H, NCH), 4.49 (dd,
J=9.7,11.1 Hz, 2H, NC
HH), 4.03 (dd,
J=8.6,9.7 Hz, 2H, NCH
H), 3.60 (br s, 2H, OH
2), 2.41 (s, 6H, CH
3), 1.54 (s, 6H, OAc).
Embodiment seven:
Synthesizing of the pincerlike rhodium compound 7 of chirality bi-imidazoline:With compound
2(153 mg, 0.20 mmol) joins in the 5 mL dichloromethane solutions, adds AgOAc (134 mg, 0.80 mmol) stirring at room 36 h then.Stopped reaction, filtering and concentrating promptly gets compound
7, productive rate 82%.The experimental data of this compound: M.p.:195-197
oC. [α]
D 20=+336 (
c0.128, CHCl
3). IR (KBr):
ν3416,3167,1758,1622,1582,1536,1513,1494,1400,1326,1097,819,705,472 cm
-1.
1H NMR (400 MHz, CDCl
3): δ 7.51 (br s, 2H, OH
2), 7.32 (d,
J=7.1 Hz, 4H, ArH), 7.29-7.25 (m, 4H, ArH), 7.21-7.13 (m, 6H, ArH), 7.04 (d,
J=7.9 Hz, 4H, ArH), 6.68-6.61 (m, 3H, ArH), 4.75-4.67 (m, 2H, NCH), 4.14-4.05 (m, 2H, NC
HH), 3.83 (dd,
J=7.4,9.6 Hz, 2H, NCH
H), 3.65 (dd,
J=3.9,13.7 Hz, 2H, PhCH
2), 2.86 (dd,
J=9.1,13.7 Hz, 2H, PhCH
2), 2.37 (s, 6H, CH
3), 1.83 (s, 6H, OAc).
Embodiment eight:
Synthesizing of the pincerlike rhodium compound 8 of chirality bi-imidazoline:With compound
3(174 mg, 0.20 mmol) joins in the 5 mL chloroformic solutions, adds AgOAc (134 mg, 0.80 mmol) stirring at room 48 h then.Stopped reaction, filtering and concentrating promptly gets compound
8, productive rate 92%.The experimental data of this compound: M.p.:151-153
oC. [α]
D 20=-14.0 (
c0.142, CHCl
3). IR (KBr):
ν3417,3172,2928,2854,1758,1626,1531,1488,1400,1320,1095,758,698,472 cm
-1.
1H NMR (400 MHz, CDCl
3): δ 7.80 (d,
J=8.0 Hz, 2H, ArH), 7.37 (t,
J=7.9 Hz, 1H, ArH), 7.28-7.22 (m, 16H, ArH), 7.18-7.15 (m, 4H, ArH), 4.87 (d,
J=4.7 Hz, 2H, NCH), 4.82 (d,
J=4.7 Hz, 2H, NCH), 4.63 (br s, 2H, OH
2), 4.51-4.45 (m, 2H, NCy-H), 2.04-1.75 (m, 6H, CyH), 1.69-1.53 (m, 6H, CyH), 1.40 (s, 6H, OAc), 1.35-1.24 (m, 2H, CyH), 1.00-0.84 (m, 6H, CyH).
Embodiment nine:
Synthesizing of the pincerlike rhodium compound 9 of chirality bi-imidazoline:With compound
4(178 mg, 0.20 mmol) joins in the 5 mL dichloromethane solutions, adds AgOAc (166 mg, 1.0 mmol) stirring at room 48 h then.Stopped reaction, filtering and concentrating promptly gets compound
9, productive rate 85%.The experimental data of this compound: M.p.:255-258
oC. [α]
D 20=+198 (
c0.104, CHCl
3). IR (KBr):
ν3416,3197,3030,2922,1628,1575,1534,1485,1403,1318,1158,1108,1018,751,696 cm
-1.
1H NMR (400 MHz, CDCl
3): δ 7.36-7.25 (m, 18H, ArH), 7.24-7.20 (m, 5H, ArH), 7.10 (br s, 5H, ArH), 6.76-6.72 (m, 1H, ArH), 6.69-6.66 (m, 2H, ArH), 5.21 (d,
J=6.5 Hz, 2H, NCH), 5.10 (br s, 2H, OH
2), 4.90 (d,
J=6.5 Hz, 2H, NCH), 2.34 (s, 6H, CH
3), 1.58 (s, 6H, OAc).
Embodiment ten:
Synthesizing of the pincerlike rhodium compound 10 of chirality bi-imidazoline:With compound
5(187 mg, 0.20 mmol) joins in the 5 mL chloroformic solutions, adds AgOAc (134 mg, 0.80 mmol) stirring at room 24 h then.Stopped reaction, filtering and concentrating promptly gets compound
10, productive rate 90%.The experimental data of this compound: M.p.:269-271
oC. [α]
D 20=+160 (
c0.124, CHCl
3). IR (KBr):
ν3416,3165,3031,2924,2361,1757,1630,1590,1488,1396,1326,1104,821,758,696 cm
-1.
1H NMR (400 MHz, CDCl
3): δ 7.48 (s, 2H, ArH), 7.32-7.28 (m, 18H, ArH), 7.22-7.01 (m, 8H, ArH), 6.81 (br s, 2H, ArH), 5.17 (d,
J=7.0 Hz, 2H, NCH), 5.16 (br s, 2H, OH
2), 4.97 (d,
J=7.0 Hz, 2H, NCH), 2.37 (s, 6H, CH
3), 1.59 (s, 6H, OAc).
Embodiment 11:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 7.8 mg (5 mol%) chirality bi-imidazoline
6Make catalyzer, 2 mL ether are made solvent, and argon shield adds trifluoroacetone acetoacetic ester (0.20 mmol, 27.0 μ L) down then, and phenylacetylene (0.24 mmol, 26.5 μ L) is in 25
oC reacts 24 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=2/1 obtains product 53.8 mg (99% yield, 97% ee).Use Daicel AD-H post to analyze enantiomeric purity: normal hexane/Virahol=99/1, flow velocity=1.0 ml/min, RT: 27.1 minutes (main enantiomorph), 33.1 minutes.
1H?NMR?(400?MHz,?CDCl
3):?δ?7.50-7.48?(m,?2H,?Ar-H),?7.40-7.30?(m,?3H,?Ar-H),?4.52-4.39?(m,?2H,?OC
H 2CH
3),?4.36?(br?s,?1H,?OH),?1.38?(t,?
J?=?7.1?Hz,?3H,?OCH
2C
H 3)。
Embodiment 12:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 4.7 mg (3 mol%) chirality bi-imidazoline
6Make catalyzer, 2 mL ether are made solvent, and argon shield adds trifluoroacetone acetoacetic ester (0.20 mmol, 27.0 μ L) down then, and phenylacetylene (0.24 mmol, 26.5 μ L) is in 25
oC reacts 24 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=2/1 obtains product 53.3 mg (98% yield, 97% ee).
Embodiment 13:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 4.7 mg (3 mol%) chirality bi-imidazoline
6Make catalyzer, 2 mL methylene dichloride are made solvent, and argon shield adds trifluoroacetone acetoacetic ester (0.20 mmol, 27.0 μ L) down then, and phenylacetylene (0.24 mmol, 26.5 μ L) is in 10
oC reacts 24 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=2/1 obtains product 13.1 mg (24% yield, 95% ee).
Embodiment 14:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 4.7 mg (3 mol%) chirality bi-imidazoline
6Make catalyzer, 2 mL ether are made solvent, and argon shield adds trifluoroacetone acetoacetic ester (0.20 mmol, 27.0 μ L) down then, and phenylacetylene (0.24 mmol, 26.5 μ L) is in 10
oC reacts 24 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=2/1 obtains product 33.7 mg (62% yield, 98% ee).
Embodiment 15:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 4.7 mg (3 mol%) chirality bi-imidazoline
6Make catalyzer, 2 mL THFs are made solvent, and argon shield adds trifluoroacetone acetoacetic ester (0.20 mmol, 27.0 μ L) down then, and phenylacetylene (0.24 mmol, 26.5 μ L) is in 25
oC reacts 24 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=2/1 obtains product 11.4 mg (21% yield, 88% ee).
Embodiment 16:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 5.6 mg (3 mol%) chirality bi-imidazoline
9Make catalyzer, 2 mL ether are made solvent, and argon shield adds trifluoroacetone acetoacetic ester (0.20 mmol, 27.0 μ L) down then, and phenylacetylene (0.24 mmol, 26.5 μ L) is in 25
oC reacts 24 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=2/1 obtains product 53.9 mg (99% yield, 97% ee).
Embodiment 17:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 5.9 mg (3 mol%) chirality bi-imidazoline
10Make catalyzer, 2 mL ether are made solvent, and argon shield adds trifluoroacetone acetoacetic ester (0.20 mmol, 27.0 μ L) down then, and phenylacetylene (0.24 mmol, 26.5 μ L) is in 25
oC reacts 24 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=2/1 obtains product 54.0 mg (99% yield, 98% ee).
Embodiment 18:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 5.9 mg (3 mol%) chirality bi-imidazoline
10Make catalyzer, 2 mL anhydrous diethyl ethers are made solvent, and argon shield adds trifluoroacetone acetoacetic ester (0.20 mmol, 27.0 μ L), 4-anisole acetylene (0.24 mmol, 31.0 μ L), 25 down then
oC reacts 24 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=2/1 obtains product 59.8 mg (99% yield, 98% ee).Use Daicel OD-H post to analyze enantiomeric purity: normal hexane/Virahol=97/3, flow velocity=0.5 ml/min, RT: 24.7 minutes (main enantiomorph), 29.1 minutes.
1H?NMR?(400?MHz,?CDCl
3):?δ?7.45-7.42?(m,?2H,?Ar-H),?6.87-6.83?(m,?2H,?Ar-H),?4.52-4.39?(m,?2H,?OC
H 2CH
3),?4.29?(br?s,?1H,?OH),?3.82?(s,?3H,?OCH
3),?1.39?(t,?
J?=?7.1?Hz,?3H,?OCH
2C
H 3).
Embodiment 19:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 4.7 mg (3 mol%) chirality bi-imidazoline
6Make catalyzer, 2 mL anhydrous diethyl ethers are made solvent, and argon shield adds trifluoroacetone acetoacetic ester (0.20 mmol, 27.0 μ L), 4-anisole acetylene (0.24 mmol, 31.0 μ L), 25 down then
oC reacts 24 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=2/1 obtains product 51.9mg (86% yield, 83% ee).
Embodiment 20:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 4.9 mg (3 mol%) chirality bi-imidazoline
7Make catalyzer, 2 mL anhydrous diethyl ethers are made solvent, and argon shield adds trifluoroacetone acetoacetic ester (0.20 mmol, 27.0 μ L), 4-anisole acetylene (0.24 mmol, 31.0 μ L), 25 down then
oC reacts 24 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=2/1 obtains product 50.7 mg (84% yield, 75% ee).
Embodiment 21:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 5.5 mg (3 mol%) chirality bi-imidazoline
8Make catalyzer, 2 mL anhydrous diethyl ethers are made solvent, and argon shield adds trifluoroacetone acetoacetic ester (0.20 mmol, 27.0 μ L), 4-anisole acetylene (0.24 mmol, 31.0 μ L), 25 down then
oC reacts 24 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=2/1 obtains product 21.7 mg (36% yield, 97% ee).
Embodiment 22:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 5.6 mg (3 mol%) chirality bi-imidazoline
9Make catalyzer, 2 mL anhydrous diethyl ethers are made solvent, and argon shield adds trifluoroacetone acetoacetic ester (0.20 mmol, 27.0 μ L), 4-anisole acetylene (0.24 mmol, 31.0 μ L), 25 down then
oC reacts 24 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=2/1 obtains product 53.7 mg (89% yield, 97% ee).
Embodiment 23:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 5.9 mg (3 mol%) chirality bi-imidazoline
10Make catalyzer, 2 mL anhydrous diethyl ethers are made solvent, and argon shield adds trifluoroacetone acetoacetic ester (0.20 mmol, 27.0 μ L) down then, and 2-fluorobenzene acetylene (0.24 mmol, 27.2 μ L) is in 25
oC reacts 24 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=2/1 obtains product 49.9 mg (86% yield,>99% ee).Use Daicel OD-H post to analyze enantiomeric purity: normal hexane/Virahol=300/1, flow velocity=0.25 ml/min, RT: 97.7 minutes, 104.4 minutes (main enantiomorph).
1H?NMR?(400?MHz,?CDCl
3):?δ?7.51-7.47?(m,?1H,?Ar-H),?7.41-7.35?(m,?1H,?Ar-H),?7.15-7.07?(m,?2H,?Ar-H),?4.47?(q,?
J?=?7.1?Hz,?2H,?OC
H 2CH
3),?4.33?(br?s,?1H,?OH),?1.40?(t,?
J?=?7.1?Hz,?3H,?OCH
2C
H 3).
Embodiment 24:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 5.6 mg (3 mol%) chirality bi-imidazoline
9Make catalyzer, 2 mL anhydrous diethyl ethers are made solvent, and argon shield adds trifluoroacetone acetoacetic ester (0.20 mmol, 27.0 μ L), 3-bromobenzene acetylene (0.24 mmol, 29.0 μ L), 25 down then
oC reacts 24 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=2/1 obtains product 58.1 mg (83% yield, 97% ee).Use Daicel OD-H post to analyze enantiomeric purity: normal hexane/Virahol=99/1, flow velocity=0.5 ml/min, RT: 24.3 minutes (main enantiomorph), 27.9 minutes.
1H?NMR?(400?MHz,?CDCl
3):?δ?7.65?(s,?1H,?Ar-H),?7.52?(d,?
J?=?7.9?Hz,?1H,?Ar-H),?7.43?(d,?
J?=?7.9?Hz,?1H,?Ar-H),?7.21?(t,?
J?=?7.9?Hz,?1H,?Ar-H),?4.54-4.40?(m,?2H,?OC
H 2CH
3),?4.31?(br?s,?1H,?OH),?1.40?(t,?
J?=?7.1?Hz,?3H,?OCH
2C
H 3).
Embodiment 25:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 5.6 mg (3 mol%) chirality bi-imidazoline
9Make catalyzer, 2 mL anhydrous diethyl ethers are made solvent, and argon shield adds trifluoroacetone acetoacetic ester (0.20 mmol, 27.0 μ L), 2-thiophene acetylene (0.24 mmol, 24.0 μ L), 25 down then
oC reacts 24 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=2/1 obtains product 46.1 mg (83% yield,>99% ee).Use Daicel OD-H post to analyze enantiomeric purity: normal hexane/Virahol=300/1, flow velocity=0.8 ml/min, RT: 41.0 minutes, 46.2 minutes (main enantiomorph).
1H?NMR?(400?MHz,?CDCl
3):?δ?7.35-7.33?(m,?2H,?Ar-H),?6.99?(dd,?
J?=?5.0,?3.8?Hz,?1H,?Ar-H),?4.53-4.39?(m,?2H,?OC
H 2CH
3),?4.34?(br?s,?1H,?OH),?1.39?(t,?
J?=?7.1?Hz,?3H,?OCH
2C
H 3).
Embodiment 26:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 5.9 mg (3 mol%) chirality bi-imidazoline
10Make catalyzer, 2 mL anhydrous diethyl ethers are made solvent, and argon shield adds trifluoropropyl ketone acid methyl esters (0.20 mmol, 20.5 μ L), 3-methylbenzene acetylene (0.24 mmol, 31.0 μ L), 25 down then
oC reacts 24 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=2/1 obtains product 49.5 mg (91% yield, 95% ee).Use Daicel OD-H post to analyze enantiomeric purity: normal hexane/Virahol=99/1, flow velocity=0.5 ml/min, RT: 31.7 minutes (main enantiomorph), 36.3 minutes.
1H?NMR?(400?MHz,?CDCl
3):?δ?7.33-7.30?(m,?2H,?Ar-H),?7.24-7.18?(m,?2H,?Ar-H),?4.28?(br?s,?1H,?OH),?4.01?(s,?3H,?COOCH
3),?2.33?(s,?3H,?CH
3).
Embodiment 27:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 5.9 mg (3 mol%) chirality bi-imidazoline
10Make catalyzer, 2 mL anhydrous diethyl ethers are made solvent, and argon shield adds trifluoropropyl ketone acid methyl esters (0.20 mmol, 20.5 μ L), 2-thiophene acetylene (0.24 mmol, 24.0 μ L), 25 down then
oC reacts 24 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=2/1 obtains product 47.5 mg (90% yield,>99% ee).Use Daicel OD-H post to analyze enantiomeric purity: normal hexane/Virahol=300/1, flow velocity=0.8 ml/min, RT: 62.8 minutes, 68.2 minutes (main enantiomorph).
1H?NMR?(400?MHz,?CDCl
3):?δ?7.34-7.33?(m,?2H,?Ar-H),?7.00-6.99?(m,?1H,?Ar-H),?4.28?(br?s,?1H,?OH),?4.00?(s,?3H,?CH
3).
Embodiment 28:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 5.6 mg (3 mol%) chirality bi-imidazoline
9Make catalyzer, 2 mL anhydrous diethyl ethers are made solvent, and argon shield adds trifluoroacetone acetoacetic ester (0.20 mmol, 27.0 μ L), 4-aldehyde radical phenylacetylene (0.24 mmol, 31.0 μ L), 25 down then
oC reacts 24 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=5/1 obtains product 45.0 mg (75% yield, 96% ee).Use Daicel AD-H post to analyze enantiomeric purity: normal hexane/Virahol=97/3, flow velocity=1.5 ml/min, RT: 28.5 minutes (main enantiomorph), 39.0 minutes.
1H?NMR?(400?MHz,?CDCl
3):?δ?10.0?(s,?1H,?CHO),?7.87?(d,?
J?=?8.2?Hz,?2H,?Ar-H),?7.67?(d,?
J?=?8.2?Hz,?2H,?Ar-H),?4.56-4.42?(m,?2H,?OC
H 2CH
3),?4.40?(br?s,?1H,?OH),?1.41?(t,?
J?=?7.1?Hz,?3H,?OCH
2C
H 3).
Embodiment 29:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 5.6 mg (3 mol%) chirality bi-imidazoline
9Make catalyzer, 2 mL anhydrous diethyl ethers are made solvent, and argon shield adds trifluoroacetone acetoacetic ester (0.20 mmol, 27.0 μ L), naphthalene acetylene (0.24 mmol, 36.5 μ L), 25 down then
oC reacts 24 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=1/1 obtains product 57.3 mg (89% yield, 98% ee).Use Daicel OD-H post to analyze enantiomeric purity: normal hexane/Virahol=99/1, flow velocity=0.5 ml/min, RT: 67.1 minutes, 73.2 minutes (main enantiomorph).
1H?NMR?(400?MHz,?CDCl
3):?δ?8.26?(d,?
J?=?8.3?Hz,?1H,?Ar-H),?7.87?(dd,?
J?=?12.2,?8.3?Hz,?2H,?Ar-H),?7.75?(dd,?
J?=?7.1,?1.0?Hz,?1H,?Ar-H),?7.61-7.52?(m,?2H,?Ar-H),?7.43?(dd,?
J?=?8.2,?7.3?Hz,?1H,?Ar-H),?4.54-4.48?(m,?2H,?OC
H 2CH
3),?1.43?(t,?
J?=?7.2?Hz,?3H,?OCH
2C
H 3).
Embodiment 30:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 5.9 mg (3 mol%) chirality bi-imidazoline
10Make catalyzer, 2 mL dry toluenes are made solvent, and argon shield adds trifluoroacetone acetoacetic ester (0.20 mmol, 27.0 μ L), 4-phenyl-ethyl acetylene (0.60 mmol, 89.5 μ L), 70 down then
oC reacts 48 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=2/1 obtains product 30.0mg (50% yield, 94% ee).Use Daicel AD-H post to analyze enantiomeric purity: normal hexane/Virahol=99/1, flow velocity=1.0 ml/min, RT: 21.1 minutes (main enantiomorph), 25.0 minutes.
1H?NMR?(400?MHz,?CDCl
3):?δ?7.31-7.28?(m,?2H,?Ar-H),?7.24-7.20?(m,?3H,?Ar-H),?4.47-4.31?(m,?2H,?OC
H 2CH
3),?4.12?(br?s,?1H,?OH),?2.85?(t,?
J?=?7.4?Hz,?2H,?
CH 2CH
2Ph),?2.55?(t,?
J?=?7.4?Hz,?2H,?CH
2 CH 2Ph),?1.34?(t,?
J?=?7.1?Hz,?3H,?OCH
2C
H 3).
The embodiment hentriaconta-:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 5.9 mg (3 mol%) chirality bi-imidazoline
10Make catalyzer, 2 mL anhydrous diethyl ethers and toluene are made solvent, and argon shield adds trifluoroacetone acetoacetic ester (0.20 mmol, 27.0 μ L), 4-phenyl-ethyl acetylene (0.60 mmol, 89.5 μ L), 70 down then
oC reacts 48 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=2/1 obtains product 46.2 mg (77% yield, 98% ee).
Embodiment 32:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 5.9 mg (3 mol%) chirality bi-imidazoline
10Make catalyzer, 2 mL anhydrous diethyl ethers and toluene are made solvent, and argon shield adds trifluoroacetone acetoacetic ester (0.20 mmol, 27.0 μ L), cyclopropyl acethlene (0.60 mmol, 51.0 μ L), 70 down then
oC reacts 48 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=2/1 obtains product 40.1 mg (85% yield, 85% ee).Use Daicel OD-H post to analyze enantiomeric purity: normal hexane/Virahol=99/1, flow velocity=0.2 ml/min, RT: 60.0 minutes (main enantiomorph), 65.5 minutes.
1H?NMR?(400?MHz,?CDCl
3):?δ?4.48-4.33?(m,?2H,?OC
H 2CH
3),?4.11?(br?s,?1H,?OH),?1.36?(t,?
J?=?7.1?Hz,?3H,?OCH
2C
H 3),?1.33-1.27?(m,?1H,?-C
H(CH
2)
2),?0.88-0.82?(m,?2H,?-CH(C
H 2 )
2),?0.81-0.76?(m,?2H,?-CH(C
H 2 )
2).
Embodiment 33:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 5.6 mg (3 mol%) chirality bi-imidazoline
9Make catalyzer, 2 mL anhydrous diethyl ethers are made solvent, and argon shield adds trifluoroacetone acetoacetic ester (0.20 mmol, 27.0 μ L), cyclohexenyl acetylene (0.24 mmol, 28.2 μ L), 25 down then
oC reacts 48 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=1/1 obtains product 44.2 mg (80% yield, 97% ee).Use Daicel OD-H post to analyze enantiomeric purity: normal hexane/Virahol=97/3, flow velocity=0.3 ml/min, RT: 21.1 minutes (main enantiomorph), 23.7 minutes.
1H?NMR?(400?MHz,?CDCl
3):?δ?6.28-6.26?(m,?1H,?-C=C
HCH
2),?4.49-4.36?(m,?2H,?OC
H 2CH
3),?4.19?(br?s,?1H,?OH),?2.15-2.09?(m,?4H,?-CC
H 2 ,?-C=CHC
H 2 ),?1.66-1.55?(m,?4H,?-CH
2C
H 2 ),?1.37?(t,?
J?=?7.1?Hz,?3H,?OCH
2C
H 3).
Embodiment 34:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 5.6 mg (3 mol%) chirality bi-imidazoline
9Make catalyzer, 2 mL anhydrous diethyl ethers are made solvent, and argon shield adds trifluoroacetone acetoacetic ester (0.20 mmol, 27.0 μ L), 4-phenyl-3-butene-1-alkynes (0.24 mmol, 30.7 mg), 25 down then
oC reacts 24 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=1/1 obtains product 48.8 mg (82% yield, 99% ee).Use Daicel AD-H post to analyze enantiomeric purity: normal hexane/Virahol=97/3, flow velocity=1.0 ml/min, RT: 17.0 minutes (main enantiomorph), 24.2 minutes.
1H?NMR?(400?MHz,?CDCl
3):?δ?7.40-7.31?(m,?5H,?Ar-H),?7.09?(d,?
J?=?16.4?Hz,?1H,?-CH=C
H),?6.15?(d,?
J?=?16.4?Hz,?1H,?-C
H=CH),?4.53-4.38?(m,?2H,?OC
H 2CH
3),?1.39?(t,?
J?=?7.1?Hz,?3H,?OCH
2C
H 3).
Embodiment 35:
In the Schlenk of 10 mL reaction tubes, add the pincerlike rhodium compound of 5.9 mg (3 mol%) chirality bi-imidazoline
10Make catalyzer, 2 mL anhydrous diethyl ethers and toluene are made solvent, and argon shield adds trifluoroacetone acetoacetic ester (0.20 mmol, 27.0 μ L), 3,3-dimethyl--ethyl acetylene (0.60 mmol, 74.0 mg), 70 down then
oC reacts 48 h.Stopped reaction concentrates, and thin-layer chromatography separates, and methylene dichloride/sherwood oil=1/1 obtains product 34.3 mg (68% yield, 95% ee).Use Daicel OD-H post to analyze enantiomeric purity: normal hexane/Virahol=99.5/0.5, flow velocity=0.1 ml/min, RT: 30.7 minutes (main enantiomorph), 34.3 minutes.
1H?NMR?(400?MHz,?CDCl
3):?δ?4.45-4.37?(m,?2H,?OC
H 2CH
3),?4.11?(br?s,?1H,?OH),?1.36?(t,?
J?=?7.1?Hz,?3H,?OCH
2C
H 3),?1.24?(s,?9H,?C(CH
3)
3)。
Claims (9)
1. the pincerlike rhodium compound of one type of chirality bi-imidazoline is characterized in that: for the compound shown in the following formula (I):
Formula (I)
R is hydrogen, nitro or halogen in the formula (I); R
1Be hydrogen, benzyl, optional alkyl or optional aryl with substituent 6-12 carbon with substituent 1-6 carbon; R
2Be hydrogen or optional aryl with substituent 6-12 carbon; R
3For choosing the alkyl with substituent 1-6 carbon, optional naphthenic base or optional aryl wantonly with substituent 6-12 carbon with substituent 3-6 carbon; X is cl ions or acetate ion, and the substituting group on abovementioned alkyl, naphthenic base or the aryl is the alkyl of 1-6 carbon, the naphthenic base of 3-6 carbon or the aryl of 6-12 carbon.
2. the pincerlike rhodium compound of chirality bi-imidazoline as claimed in claim 1; It is characterized in that: described optional alkyl with substituent 1-6 carbon is methyl, sec.-propyl, the tertiary butyl, sec.-butyl or isobutyl-, and optional naphthenic base with substituent 3-6 carbon is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl; Described optional aryl with substituent 6-12 carbon is phenyl, p-methylphenyl or p-methoxyphenyl, to ethoxyl phenenyl, 2,6-diisopropyl phenyl or right-chloro-phenyl-.
3. according to claim 1 or claim 2 the preparation method of the pincerlike rhodium compound of chirality bi-imidazoline; It is characterized in that: with bi-imidazoline base benzene-like compounds between chirality; With three rhodium trichloride hydrate reacting by heating, solvent evaporated, thin-layer chromatography separation and purification promptly get the chirality bi-imidazoline pincer rhodium compound of the formula that X is a cl ions (I) then in solvent, in the presence of the alkali; Then add Silver monoacetate solution, stirring at room, filtering and concentrating promptly get the pincerlike rhodium compound of chirality bi-imidazoline of the formula that X is an acetate ion (I), and bi-imidazoline base benzene-like compounds is between described chirality:
4. the preparation method of the pincerlike rhodium compound of chirality bi-imidazoline as claimed in claim 3, it is characterized in that: the mole dosage of a bi-imidazoline base benzene-like compounds, alkali is 1 ~ 1.5 times of three rhodium trichloride hydrate mole dosage; Solvent is that ethanol, methyl alcohol or volume ratio are the methanol-water mixed solvent of 10 ~ 20:1; Alkali is triethylamine or sodium hydrogencarbonate; Heating temperature is 60 ~ 80
oC; Be 12 ~ 48 h heat-up time.
5. like the preparation method of claim 3 or the pincerlike rhodium compound of 4 described chirality bi-imidazolines, it is characterized in that: Silver monoacetate solution is the methylene dichloride or the chloroformic solution of Silver monoacetate; The mole dosage of Silver monoacetate is that X is 2 ~ 5 times of the pincerlike rhodium compound of chirality bi-imidazoline of the formula (I) of halide-ions; The stirring at room time is 24 ~ 48 h.
6. the compound method of optical activity trifluoromethyl alkynes third tertiary alcohol is characterized in that: use according to claim 1 or claim 2 the pincerlike rhodium compound of chirality bi-imidazoline as catalyzer; The synthetic following steps that adopt: said rhodium catalyst, trifluoroacetone acid esters and end-group alkyne are joined in the organic solvent, and concentrated and purified optical activity trifluoromethyl alkynes third tertiary alcohol that promptly gets that finishes is reacted in reaction under argon shield.
7. the compound method of optical activity trifluoromethyl alkynes third tertiary alcohol as claimed in claim 6, it is characterized in that: the structure of trifluoroacetone acid esters is:
，
Wherein, R
4Be methyl or ethyl; The structure of end-group alkyne does
, wherein, R
5Naphthenic base, cyclohexenyl, naphthyl, thienyl or R for the alkyl of 1-6 carbon, styroyl, styryl, 3-6 carbon
6Substituted phenyl, described R
6Substituted phenyl, R
6Be hydrogen, methyl, ethyl, the tertiary butyl, methoxyl group, fluorine, chlorine, bromine, trifluoromethyl, nitro or aldehyde radical, R
6The position of substitution on phenyl ring is ortho position, a position or contraposition.
8. the compound method of optical activity trifluoromethyl alkynes third tertiary alcohol as claimed in claim 6 is characterized in that: the mole dosage ratio that feeds intake of said rhodium catalyst, end-group alkyne and trifluoroacetone acid esters is 0.01 ~ 0.05:1.2 ~ 3.0:1.0; Described organic solvent is the mixed solvent of methylene dichloride, THF, ether, Di Iso Propyl Ether, toluene or toluene-ether; Temperature of reaction is 10 ~ 70
oC; Reaction times is 24 ~ 48 h.
9. the compound method of optical activity trifluoromethyl alkynes third tertiary alcohol as claimed in claim 6 is characterized in that: the structure of optical activity trifluoromethyl alkynes third tertiary alcohol is:
，
Wherein, R
4Be methyl or ethyl; R
5Naphthenic base, cyclohexenyl, naphthyl, thienyl or R for the alkyl of 1-6 carbon, styroyl, styryl, 3-6 carbon
6Substituted phenyl, described R
6Substituted phenyl, R
6Be hydrogen, methyl, ethyl, the tertiary butyl, methoxyl group, fluorine, chlorine, bromine, trifluoromethyl, nitro or aldehyde radical, R
6The position of substitution on phenyl ring is ortho position, a position or contraposition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210271081.XA CN102746343B (en) | 2012-07-31 | 2012-07-31 | Chiral bis-imidazoline pincer rhodium compound, preparation and asymmetric catalysis application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210271081.XA CN102746343B (en) | 2012-07-31 | 2012-07-31 | Chiral bis-imidazoline pincer rhodium compound, preparation and asymmetric catalysis application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102746343A true CN102746343A (en) | 2012-10-24 |
| CN102746343B CN102746343B (en) | 2015-06-03 |
Family
ID=47026881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210271081.XA Active CN102746343B (en) | 2012-07-31 | 2012-07-31 | Chiral bis-imidazoline pincer rhodium compound, preparation and asymmetric catalysis application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102746343B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015159225A1 (en) * | 2014-04-15 | 2015-10-22 | The University Of North Carolina At Chapel Hill | Bis(phosphine)-carbodicarbene catalyst complexes and methods of using the same |
| CN105152967A (en) * | 2015-09-28 | 2015-12-16 | 方美兰 | Synthesis method for medical intermediate trifluoromethyl substituted cyclohexane compound |
| CN113559939A (en) * | 2019-04-22 | 2021-10-29 | 郑州大学 | Alpha alkylation reaction catalyst for nitrile and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0236182A (en) * | 1988-07-26 | 1990-02-06 | Mitsui Toatsu Chem Inc | Novel rhodium complex, production thereof and method for producing asymmetric alcohol using said novel rhodium complex |
| JPH04279583A (en) * | 1991-03-08 | 1992-10-05 | Mitsui Toatsu Chem Inc | Rhodium complex of optically active 4-substituted-2,6-bis(oxazolyl)pyridine derivative and production of asymmetric alcohol using the same complex |
| CN101012198A (en) * | 2007-01-29 | 2007-08-08 | 郑州大学 | Chiral and non-chiral diimidazolinylbenzene compounds and synthesis method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4279583B2 (en) * | 2003-03-28 | 2009-06-17 | シーケーディ株式会社 | Actuator |
-
2012
- 2012-07-31 CN CN201210271081.XA patent/CN102746343B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0236182A (en) * | 1988-07-26 | 1990-02-06 | Mitsui Toatsu Chem Inc | Novel rhodium complex, production thereof and method for producing asymmetric alcohol using said novel rhodium complex |
| JPH04279583A (en) * | 1991-03-08 | 1992-10-05 | Mitsui Toatsu Chem Inc | Rhodium complex of optically active 4-substituted-2,6-bis(oxazolyl)pyridine derivative and production of asymmetric alcohol using the same complex |
| CN101012198A (en) * | 2007-01-29 | 2007-08-08 | 郑州大学 | Chiral and non-chiral diimidazolinylbenzene compounds and synthesis method |
Non-Patent Citations (3)
| Title |
|---|
| TAKASHI OHSHIMA等，: "C1-Symmetric Rh/Phebox-Catalyzed Asymmetric Alkynylation of α-Ketoesters", 《ANGEW. CHEM. INT. ED.》, vol. 50, 30 May 2011 (2011-05-30), pages 6296 - 6300, XP055001845, DOI: doi:10.1002/anie.201100252 * |
| TAKUSHI SHIOMI等，: "Intermolecular Asymmetric Reductive Aldol Reaction of Ketones as Acceptors Promoted by Chiral Rh(Phebox) Catalyst", 《ORG. LETT.》, vol. 9, no. 9, 27 March 2007 (2007-03-27), pages 1651 - 1654 * |
| YOSHINORI KANAZAWA等，: "Asymmetric Conjugate Reduction of α,β-Unsaturated Ketones and Esters with Chiral Rhodium(2,6-bisoxazolinylphenyl) Catalysts", 《CHEM. EUR. J.》, vol. 12, 29 September 2005 (2005-09-29), pages 63 - 71, XP009064275, DOI: doi:10.1002/chem.200500841 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015159225A1 (en) * | 2014-04-15 | 2015-10-22 | The University Of North Carolina At Chapel Hill | Bis(phosphine)-carbodicarbene catalyst complexes and methods of using the same |
| CN105152967A (en) * | 2015-09-28 | 2015-12-16 | 方美兰 | Synthesis method for medical intermediate trifluoromethyl substituted cyclohexane compound |
| CN113559939A (en) * | 2019-04-22 | 2021-10-29 | 郑州大学 | Alpha alkylation reaction catalyst for nitrile and preparation method thereof |
| CN113559939B (en) * | 2019-04-22 | 2023-06-23 | 郑州大学 | Alpha alkylation reaction catalyst of nitrile and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102746343B (en) | 2015-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Asymmetric Lewis acid catalysis directed by octahedral rhodium centrochirality | |
| Chelucci et al. | Ruthenium and osmium complexes containing 2-(aminomethyl) pyridine (Ampy)-based ligands in catalysis | |
| Eitel et al. | Asymmetric Michael additions of α-cyanoacetates by soft Lewis acid/hard Brønsted acid catalysis: stereodivergency with bi-vs. monometallic catalysts | |
| Fujimori et al. | Stereoselective conjugate addition reactions using in situ metallated terminal alkynes and the development of novel chiral P, N-ligands | |
| Batuecas et al. | Catalytic asymmetric C–H arylation of (η6-arene) chromium complexes: facile access to planar-chiral phosphines | |
| Hwang et al. | Enantioselective addition of diethylzinc to aldehydes induced by a new chiral Ti (IV) catalyst | |
| US6486337B2 (en) | Ruthenium-disphosphine complexes and their use as catalysts | |
| Chapman et al. | Enantioselective rhodium-catalysed addition of boronic acids using C2-symmetric aryl diphosphite ligands | |
| Huang et al. | Asymmetric Synthesis of Chiral Spiroketal Bisphosphine Ligands and Their Application in Enantioselective Olefin Hydrogenation | |
| Sanjeevakumar et al. | Highly enantioselective Henry reaction catalyzed by a new chiral C2-symmetric N, N′-bis (isobornyl) ethylenediamine–copper complex | |
| CN102746343B (en) | Chiral bis-imidazoline pincer rhodium compound, preparation and asymmetric catalysis application thereof | |
| Patti | Green approaches to asymmetric catalytic synthesis | |
| Wu et al. | Novel planar chiral P, N-[2.2] paracyclophane ligands: synthesis and application in palladium-catalyzed allylic alkylation | |
| He et al. | Synthesis of some new chiral bifunctional o-hydroxyarylphosphonodiamides and their application as ligands in Ti (IV) complex catalyzed asymmetric silylcyanation of aromatic aldehydes | |
| Tato et al. | Rhodium-catalyzed conjugate addition of arylindium reagents to α, β-unsaturated carbonyl compounds | |
| Pizzuti et al. | Enantioselective alkynylation and phenylation of aromatic aldehydes promoted by atropisomeric 1, 1′-binaphthylazepine-based amino alcohols | |
| Chen et al. | Synthesis, structure, and catalytic activity of titanium complexes with chiral biaryl Schiff-base ligands | |
| Kagan et al. | PREPARATION OF CHIRAL FERROCENES BY ASYNAMETRIC SYNTHESIS OR BY KINETIC RESOLUTION | |
| Xu et al. | Asymmetric addition of phenylacetylene to aldehydes catalyzed by β‐sulfonamide alcohol‐titanium complex | |
| Hu et al. | Synthesis of novel P-ketimine bidentate ferrocenyl ligands with central and planar chirality and comparsion in the catalytic activity between P-ketimine and P-aldimine | |
| Arroyo et al. | Synthesis of a new class of chiral aminoalcohols and their application in the enantioselective addition of diethylzinc to aldehydes | |
| US7906669B2 (en) | Metallocene-based phosphorus chiral phosphines | |
| CN103910676B (en) | A kind of synthetic method of polysubstituted tetrahydro isoquinoline derivative | |
| Sun et al. | Synthesis of new Schiff base-camphorsulfonyl amide ligands and in situ screening in the asymmetric additions of organozinc reagents to aldehydes | |
| JP2000136193A (en) | Optically acitive bisphosphinomethane and assymetric synthesis using its phodium or copper complex |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170301 Address after: 100176 Beijing economic and Technological Development Zone, Tai Po Road, No. 6 Patentee after: Kanglong (Beijing) new drug technology Limited by Share Ltd Address before: 450001 Zhengzhou science and Technology Development Zone, Henan, No. 100 science Avenue Patentee before: Zhengzhou University |