CN105541918B - A kind of chirality 5,5,10,10 4 aryl two ring [4.4.0] 3,8 bis phosphoric acid and its preparation method and application - Google Patents
A kind of chirality 5,5,10,10 4 aryl two ring [4.4.0] 3,8 bis phosphoric acid and its preparation method and application Download PDFInfo
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- CN105541918B CN105541918B CN201610060866.0A CN201610060866A CN105541918B CN 105541918 B CN105541918 B CN 105541918B CN 201610060866 A CN201610060866 A CN 201610060866A CN 105541918 B CN105541918 B CN 105541918B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 title claims abstract 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title abstract description 34
- 229910000147 aluminium phosphate Inorganic materials 0.000 title abstract description 17
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- -1 aryl erythrol Chemical compound 0.000 claims abstract description 22
- 229910019213 POCl3 Inorganic materials 0.000 claims abstract description 12
- 150000007530 organic bases Chemical class 0.000 claims abstract description 9
- 230000003287 optical effect Effects 0.000 claims abstract description 5
- 150000003899 tartaric acid esters Chemical class 0.000 claims abstract description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 36
- 150000003016 phosphoric acids Chemical class 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 20
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 7
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 230000033228 biological regulation Effects 0.000 claims description 5
- 125000001624 naphthyl group Chemical group 0.000 claims description 5
- 229940095064 tartrate Drugs 0.000 claims description 5
- UJHSIDUUJPTLDY-UHFFFAOYSA-N (2-nitrophenyl)-phenylmethanone Chemical compound [O-][N+](=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 UJHSIDUUJPTLDY-UHFFFAOYSA-N 0.000 claims description 4
- 125000004799 bromophenyl group Chemical group 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- YSAVZVORKRDODB-UHFFFAOYSA-N Diethyl tartrate Chemical group CCOC(=O)C(O)C(O)C(=O)OCC YSAVZVORKRDODB-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims 1
- 229960001826 dimethylphthalate Drugs 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 9
- 230000006698 induction Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005761 Biginelli synthesis reaction Methods 0.000 description 5
- OWVIRVJQDVCGQX-VSGBNLITSA-N [(4r,5r)-5-[hydroxy(diphenyl)methyl]-2,2-dimethyl-1,3-dioxolan-4-yl]-diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)([C@H]1[C@@H](OC(O1)(C)C)C(O)(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 OWVIRVJQDVCGQX-VSGBNLITSA-N 0.000 description 5
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- BVUQKCCKUOSAEV-UHFFFAOYSA-M magnesium;methylbenzene;bromide Chemical compound [Mg+2].[Br-].CC1=CC=[C-]C=C1 BVUQKCCKUOSAEV-UHFFFAOYSA-M 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical class C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001212 derivatisation Methods 0.000 description 2
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- AFINAILKDBCXMX-PBHICJAKSA-N (2s,3r)-2-amino-3-hydroxy-n-(4-octylphenyl)butanamide Chemical compound CCCCCCCCC1=CC=C(NC(=O)[C@@H](N)[C@@H](C)O)C=C1 AFINAILKDBCXMX-PBHICJAKSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- DBLYWAKCUDNYPJ-UHFFFAOYSA-N C(C(O)C(O)C(=O)O)(=O)O.P(=O)(O)(O)O.P(=O)(O)(O)O Chemical compound C(C(O)C(O)C(=O)O)(=O)O.P(=O)(O)(O)O.P(=O)(O)(O)O DBLYWAKCUDNYPJ-UHFFFAOYSA-N 0.000 description 1
- 241000819038 Chichester Species 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 229910010084 LiAlH4 Inorganic materials 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XFDJMIHUAHSGKG-UHFFFAOYSA-N chlorethoxyfos Chemical compound CCOP(=S)(OCC)OC(Cl)C(Cl)(Cl)Cl XFDJMIHUAHSGKG-UHFFFAOYSA-N 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- PVRATXCXJDHJJN-UHFFFAOYSA-N dimethyl 2,3-dihydroxybutanedioate Chemical compound COC(=O)C(O)C(O)C(=O)OC PVRATXCXJDHJJN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002576 ketones Chemical group 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000010490 three component reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0257—Phosphorus acids or phosphorus acid esters
- B01J31/0258—Phosphoric acid mono-, di- or triesters ((RO)(R'O)2P=O), i.e. R= C, R'= C, H
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B53/00—Asymmetric syntheses
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of chiral 5,5,10,10 four aryl two ring [4.4.0] 3,8 bis phosphoric acid and its preparation method and application, the general structure of the chipal compounds is as follows：Its preparation method is as follows：Optical pure tartaric acid ester and RMgBr are reacted, chirality 1,1 is made, 4,4 four aryl erythrol, under organic base existence condition, by chirality 1, Isosorbide-5-Nitrae, 4 four aryl erythrol occur the cycli phosphateization of high regioselectivity 1,3 at 0 DEG C 36 DEG C with POCl3 and reacted, and chirality 5 is made, 5, the bis phosphoric acid of the ring of 10,10 tetraphenyl two [4.4.0] 3,8.The bis phosphoric acid of 5,5,10,10 four aryl of chirality, two ring [4.4.0] 3,8 has excellent chiral induction ability, can be used to be catalyzed asymmetric syntheses.This method raw material is easy to get, and technological process is simple, easy to operate, good reaction selectivity, product yield high.
Description
Technical field
The present invention relates to chipal compounds preparing technical field, and in particular to a kind of chirality ring of 5,5,10,10- tetra- aryl two
[4.4.0] -3,8- bis phosphoric acids and its preparation method and application.
Background technology
Chiral phosphoric acid is as one kind of Br φ nsted acid catalysts, the acidity with moderate strength, the rigidity knot of ring-type
Structure, shows excellent asymmetry catalysis activity, a kind of general chiral catalyst [Terada is had developed at present
M.Bulletin of the Chemical Society of Japan,2010,83(2):101-119.], part chiral phosphoric acid
It has been commercialized.Chiral phosphoric acid catalyst is in catalysis asymmetric Mannich reaction [(a) Akiyama, T.；Itoh,J.；
Yokota,K.；Fuchibe,K.Angew.Chem.Int.Ed.2004,43,1566；(b)Uraguchi,D.；Terada,
M.J.Am.Chem.Soc.2004,126,5356.], C-H activation [(a) Mori, K.；Ehara,K.；Kurihara,K.；
Akiyama,T.J.Am.Chem.Soc.2011,133,6166-6169.(b)Terada,M.；Soga,K.；Momiyama,
N.Angew.Chem., Int.Ed., 2008,47,4122-4125.], asymmetric Friedel-Crafts reaction [(a) Bi B,
Lou Q-X,Ding Y-Y,Chen S-W,Zhang S-S,Hu W-H,Zhao J-L.Org.Lett.,2015,17(3),540–
543. (b) Mori K, Wakazawa M, Akiyama T.Chem.Sci., 2014,5,1799-1803.], it is asymmetric
Biginelli reacts [Li, N.；Chen,X.H.；Song,J.；Luo,S.W.；Fan,W.；Gong,
L.Z.J.Am.Chem.Soc.2009,131,15301-15310.(b)Chen,X.H.；Xu,X.Y.；Liu,H.；Cun,L.F.；
Gong,L.Z.J.Am.Chem.Soc.2006,128,14802-14803.(c)Goss,J.M.；Schaus,
S.E.J.Org.Chem.2008,73 (16), 7651-7656.] in terms of the result that has achieved.It is chiral single but research is found
Phosphoric acid is less efficient to certain form of catalytic reaction, the reaction time is longer and catalyst amount it is larger [(a) Terada,
M.Chem.Commun., 2008,4097-4112. (b) Terada, M.Synthesis 2010,1929-1982.], so at present
Research focus on synthesis [(a) Momiyama, N. of chiral diphosphonic acid；Konno,T.；Furiya,Y.；Iwamoto,T.；
Terada,M.J.Am.Chem.Soc.2011,133,19294-19297.(b)He,L.；Chen,X.H.；Wang,D.N.；Luo,
S.W.；Zhang,W.Q.；Yu,J.；Ren,L.；Gong,L.Z.J.Am.Chem.Soc.2011,133,13504-13518.].
The phosphorylation reaction of binaphthol derivative is easy to carry out：Binaphthol derivative can directly be made with phosphorus oxychloride reaction
.But distich naphthalene skeleton performs the derivatization cumbersome, typically first phenolic hydroxyl group is protected, then pass through metallization, halogenation
Corresponding group is introduced with Suzuki coupling reactions, then phenolic hydroxyl group is deprotected, is then made corresponding to phosphorus oxychloride reaction
Chiral phosphoric acid catalyst [Rueping, M.；Sugiono,E.；Azap,C.T.Theissmann in Catalysts for
Fine Chemical Synthesis,Vol.5(Eds.:S.M.Roberts,J.Whittall),Wiley,Chichester,
2007,pp.161-181.The synthesis has been described as part of the synthesis of
the corresponding phosphoric acid derivative.].Chiral monophosphorous acid derived from TADDOL, chiral bone
Frame is easy to perform the derivatization, but the preparation of chiral phosphoric acid is more complicated, it is necessary to which phosphorous is made in the phosphorus trichloride reaction higher with activity
Acid esters, corresponding chiral phosphoric acid [(a) Akiyama T, Saitoh can just be obtained by recycling iodine or hydrogen peroxide to be aoxidized
Y,Morita H,et al.Advanced Synthesis&Catalysis,2005,347,1523-1526.(b)Voituriez
A,Charette A B.Advanced Synthesis&Catalysis,2006,348,2363-2370.].And the secondary hydroxyls of TADDOL
The deprotection of base is cumbersome, typically first to be aoxidized with DDQ (2,3-Dichloro-5,6-dicyano-1,4-benzoquinone), then use
LiAlH4Aldehyde/ketone protection group [Luithle, J.E. is sloughed in reduction；Pietruszka,J.J.Org.Chem.1999,64,8287-
8297.], and chiral bisphosphine acid has not yet to see report derived from tartaric acid.
The content of the invention
To solve the problem of above-mentioned prior art is present, the invention provides a kind of chiral ring of 5,5,10,10- tetra- aryl two
The preparation method of [4.4.0] -3,8- bis phosphoric acids, this method raw material is easy to get, and technological process is simple, easy to operate, reaction selectivity
It is good, product yield high.Chiral ring [the 4.4.0] -3,8- bis phosphoric acids of tetra- aryl of 5,5,10,10- two have excellent chiral induction
Ability, can be used to be catalyzed asymmetric syntheses.
Realize technical scheme that above-mentioned purpose of the present invention used for：
A kind of chirality ring of 5,5,10,10- tetra- aryl two [4.4.0] -3,8- bis phosphoric acids, its general structure is as follows：
The Ar is phenyl, tolyl, chlorphenyl, bromophenyl, nitrobenzophenone or naphthyl.
A kind of preparation method of the chirality ring of 5,5,10,10- tetra- aryl two [4.4.0] -3,8- bis phosphoric acids, including following step
Suddenly：Optical pure tartaric acid ester and RMgBr are reacted, chirality 1 is made, Isosorbide-5-Nitrae, the aryl erythrol of 4- tetra- is deposited in organic base
Under conditions, by chirality 1, with POCl3 height region selection occurs under the conditions of 0 DEG C -36 DEG C for Isosorbide-5-Nitrae, the aryl erythrol of 4- tetra-
Property 1,3- cycli phosphateizations reaction, be made chirality the ring of 5,5,10,10- tetra- aryl two [4.4.0] -3,8- bis phosphoric acids, described grignard
R in reagent is phenyl, tolyl, chlorphenyl, bromophenyl, nitrobenzophenone or naphthyl.
Described tartrate is ethyl tartrate or dimethyl tartrate.
The mol ratio of tartrate and RMgBr is 1:6-8.
Described organic base is triethylamine or pyridine.
The mol ratio of organic base and the aryl erythrol of chirality 1,1,4,4- tetra- is 6-30:1.
The mol ratio of chiral the aryl erythrol of 1,1,4,4- tetra- and POCl3 is 1:2-3.
The concrete operation step of described high regioselectivity 1,3- cycli phosphateizations reaction is as follows：By chiral 1,1,4,4-
Tetraphenyl erythrol is added in reaction vessel, and organic base is then added into reaction vessel, and reaction vessel is placed in into 0-10 DEG C
In environment, after stirring 15 minutes, it is added dropwise under conditions of stirring into reaction vessel after POCl3, completion of dropping and continues to stir
30 minutes, 25-36 DEG C is heated to, after being further continued for stirring 120 minutes, with the pH value of 2mol/L hydrochloric acid regulation system to 1-2, knot
Chiral ring [4.4.0] -3,8- bis phosphoric acids of tetra- aryl of 5,5,10,10- two are obtained after crystalline substance.
A kind of ring [4.4.0] -3,8- bis phosphoric acids of tetra- aryl of chiral 5,5,10,10- two are in catalysis asymmetric catalysis synthesis
Application.
Compared with prior art, its advantage and advantage are the present invention：
1) this method raw material is easy to get, and technological process is simple, and process conditions are easy to control, easy to operate, workable, and raw
Produce cost low.
2) this method is from TADDOL parent compound-chirality 1, and Isosorbide-5-Nitrae, the aryl erythrol of 4- tetra- sets out, and passes through itself and three
The double phosphorus of ring [the 4.4.0] -3,8- of tetra- aryl of chirality 5,5,10,10- two are made in the high regioselectivity derivative reaction of chlorethoxyfos
Acid, avoids oxidation and the deprotection program of TADDOL secondary hydroxyls of phosphite ester, so as to enormously simplify its synthesis step.
3) this method conversion zone is selectively good, and product yield high, test shows, product yield is up to 87%.
4) ring [4.4.0] of 5,5,10,10- tetra- aryl of chirality two -3, the 8- bis phosphoric acids have excellent chiral induction ability,
It can be used to be catalyzed asymmetric syntheses, such as Biginelli reactions.
Brief description of the drawings
Fig. 1 is the list of (1R, 6R) -5,5,10,10- tetraphenyls two ring [4.4.0] -3,8- bis phosphoric acids prepared by embodiment 1
Crystal structure figure.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Embodiment 1
A kind of (1R, 6R) -5, the preparation method of the ring of 5,10,10- tetraphenyl two [4.4.0] -3,8- bis phosphoric acids, its step
It is：
1) phenyl-magnesium-bromide is dissolved in tetrahydrofuran, be then added drop-wise to optical voidness (2R, 3R)-ethyl tartrate
In the tetrahydrofuran solution of phenyl-magnesium-bromide, the mol ratio of wherein phenyl-magnesium-bromide and (2R, 3R)-ethyl tartrate is 6：1,
After the completion of reaction, it is quenched with saturated aqueous ammonium chloride, ether extraction, concentration obtains (2R, 3R) -1 after silica gel column chromatography,
Isosorbide-5-Nitrae, 4- tetraphenyl erythrol, yield：50%, m.p.:149-150℃；[α]D 25=+154.0 (c 1.2, CHCl3)；IR
(KBr):3436,3058,2916,1598,1492,1447,1063,698；1H-NMR(CDCl3,300MHz):δ7.37–7.13
(m,20H,Ar-H)；4.65 (d, J=7.2Hz, 2H, OH) 4.41 (d, J=4.7Hz, 2H, CH)；3.77 (d, J=5.3Hz, 2H,
OH).13C-NMR(CDCl3,75MHz)δ143.8；142.7；134.6；131.5；129.3；128.3；128.2；127.9；
127.5；126.7；125.5；81.3,69.7.
2) by (2R, 3R) -1, Isosorbide-5-Nitrae, 4- tetraphenyl erythrol is added in round-bottomed flask, is then added into round-bottomed flask
Triethylamine, wherein the mol ratio of (2R, 3R) -1, Isosorbide-5-Nitrae, 4- tetraphenyls erythrol and triethylamine is 1:30, round-bottomed flask is placed in 0
In DEG C environment, after stirring 15 minutes, be added dropwise POCl3 into round-bottomed flask under conditions of stirring, wherein POCl3 with
The mol ratio of (2R, 3R) -1,1,4,4- tetraphenyl erythrol is 2:1, continue after completion of dropping to stir 30 minutes, be heated to 25
DEG C, after being further continued for stirring 120 minutes, with the pH value of 2mol/L hydrochloric acid regulation system to 1-2, (1R, 6R) -5 are obtained after crystallization,
The ring of 5,10,10- tetraphenyls two [4.4.0] -3,8- bis phosphoric acids.Yield：87%；m.p.195-197℃；[α]D 28=-108 (c
0.7,CH3CH2OH)；1H NMR(CDCl3,300MHz):δ7.44-7.20(m,20H,Ar-H),5.52(s,2H,C-H)；4.57
(s,2H,-OH,mixed with the water peak of DMSO and disappeared after adding
D2O)；13C NMR(CDCl3,75MHz):δ142.3,140.7,129.5,129.1,128.9,128.0,126.1,125.5,
89.0,72.2。
Single crystal data:empirical formula,C28H26O9P2；formula weight,568.43；calculated
density,1.378g/cm3；volume(V),2739.3(3)；crystal system,Orthorhombic；space
group,P2(1)2(1)2(1)；Z=4；Unit cell dimensions, a=11.2864 (8), b=15.4239 (12), c
=15.7359 (11), α=90 ° β=90 °, γ=90 °；absorption coefficient(μ),0.212mm-1；index
ranges-14≤h≤10,-19≤k≤19,-20≤l≤19；F(000),1184；GOF, No. 1.072.CCDC：1435079,
Its mono-crystalline structures is as shown in Figure 1.
As the above analysis, the organic compound is (1R, 6R) -5, the ring of 5,10,10- tetraphenyl two [4.4.0] -3,8-
Bis phosphoric acid, its structural formula is as follows：
Embodiment 2
A kind of (1S, 6S) -5, the preparation method of the ring of 5,10,10- tetraphenyl two [4.4.0] -3,8- bis phosphoric acids, its step
It is：
1) preparation (2S, 3S) -1, Isosorbide-5-Nitrae, 4- tetraphenyl erythrol, its preparation method be the same as Example 1 only need to be by embodiment 1
In (2R, 3R)-ethyl tartrate be substituted for (2S, 3S)-ethyl tartrate.
2) by (2S, 3S) -1, Isosorbide-5-Nitrae, 4- tetraphenyl erythrol is added in round-bottomed flask, is then added into round-bottomed flask
Pyridine, wherein the mol ratio of (2S, 3S) -1, Isosorbide-5-Nitrae, 4- tetraphenyls erythrol and pyridine is 1:20, round-bottomed flask is placed in 10 DEG C
In environment, after stirring 15 minutes, be added dropwise POCl3 into round-bottomed flask under conditions of stirring, wherein POCl3 with (2R,
3R) mol ratio of -1,1,4,4- tetraphenyls erythrol is 2:1, continue after completion of dropping to stir 30 minutes, be heated to 36 DEG C, then
Continue after stirring 120 minutes, with the pH value of 2mol/L hydrochloric acid regulation system to 1-2, obtain (1S, 6S) -5 after crystallization, 5,10,
The ring of 10- tetraphenyls two [4.4.0] -3,8- bis phosphoric acids.Yield：82%；m.p.196-198℃；[α]D 28=+108 (c 0.8,
CH3CH2OH)；1H NMR(CDCl3,300MHz):δ7.45-7.19(m,20H,Ar-H),5.50(s,2H,C-H),3.82(s,
2H,-OH,mixed with the water peak of DMSO and disappeared after adding D2O)；13C
NMR(CDCl3,75MHz):δ141.8,140.2,128.9,128.3,127.5,125.5,125.0,88.4,71.67。
As the above analysis, the organic compound is (1S, 6S) -5, the ring of 5,10,10- tetraphenyl two [4.4.0] -3,8-
Bis phosphoric acid, its structural formula is as follows：
Embodiment 3
A kind of (1R, 6R) -5, the preparation method of the ring of 5,10,10- tetra- p-methylphenyl two [4.4.0] -3,8- bis phosphoric acids, it is walked
Suddenly it is：
1) p-tolylmagnesium bromide is dissolved in tetrahydrofuran, then dripped optical voidness (2R, 3R)-ethyl tartrate
It is added in the tetrahydrofuran solution of p-tolylmagnesium bromide, wherein p-tolylmagnesium bromide and (2R, 3R)-ethyl tartrate
Mol ratio is 8:1, after the completion of reaction, it is quenched with saturated aqueous ammonium chloride, ether extraction, concentration, after silica gel column chromatography
To the p-methylphenyl erythrol of (2R, 3R) -1,1,4,4- four.Yield：49%, m.p.:162-163℃；[α]D 25=+102.2 (c
0.5,CHCl3)；1H-NMR(CDCl3,400MHz):δ7.36–7.06(m,16H,Ar-H)；4.68(s,2H,OH)4.41(s,2H,
CH)；3.80(s,2H,OH),2.36(s,6H,CH3),2.24(s,6H,CH3).13C-NMR(CDCl3,100MHz)δ143.9；
143.1,135.8；125.4；129.0,128.5,126.7,125.8,81.4,71.8.
2) by (2R, 3R) -1, Isosorbide-5-Nitrae, the p-methylphenyl erythrol of 4- tetra- is added in round-bottomed flask, then into round-bottomed flask
Pyridine is added, wherein the mol ratio of (2R, 3R) -1, Isosorbide-5-Nitrae, the p-methylphenyl erythrol of 4- tetra- and pyridine is 1:10, by round-bottomed flask
It is placed in 0 DEG C of environment, after stirring 15 minutes, POCl3, wherein trichlorine oxygen is added dropwise into round-bottomed flask under conditions of stirring
The mol ratio of phosphorus and (2R, 3R) -1,1,4,4- tetraphenyl erythrol is 3:1, continue after completion of dropping to stir 30 minutes, be heated to
36 DEG C, after being further continued for stirring 120 minutes, with the pH value of 2mol/L hydrochloric acid regulation system to 1-2, obtained after crystallization (1R, 6R)-
Tetra- p-methylphenyls of 5,5,10,10- two ring [4.4.0] -3,8- bis phosphoric acids.Yield：82%；m.p.184-186℃；[α]D 28=-
127(c 0.5,CH3CH2OH)；1H NMR(CDCl3,400MHz):δ7.32-7.10(m,16H,Ar-H),5.49(s,2H,C-
H)；4.58(s,2H,-OH,mixed with the water peak of DMSO and disappeared after
adding D2O), 2.32 (s, 12H, CH3)；13C NMR(CDCl3,100MHz):δ142.1,141.8,129.6,129.2,
128.7,128.2,126.3,125.8,88.6,71.8。
Embodiment 4
Three groups are catalyzed with ring [the 4.4.0] -3,8- bis phosphoric acids of (1R, 6R) -5,5,10,10- tetraphenyls two prepared by embodiment 1
Divide exemplified by Biginelli reactions, chiral 5, the purposes of the ring of 5,10,10- tetra- aryl two [4.4.0] -3,8- bis phosphoric acids is done in detail
Explanation.
Test method：Ring [the 4.4.0] -3,8- bis phosphoric acids of (1R, 6R) -5,5,10,10- tetraphenyls two are with 10% catalyst
(molar ratio is 1 for consumption (10% of benzaldehyde amount of substance) catalysis benzaldehyde, ethyl acetoacetate and thiocarbamide:1.1:1.1)
Three component reactions, be stirred at room temperature after 6 days, Biginelli reaction products obtained after purification process.
Result of the test is as follows：
Yield：52%；ee>99%. [α]D 20=-68 (c 0.5, MeOH)；1H NMR(DMSO,400MHz):δ10.32
(s, 1H, NH), 9.63 (s, 1H, NH), 7.38-7.16 (m, 5H, Ar-H), 5.16 (d, J=3.6Hz, 1H, CH), 3.98 (q, J
=7.1Hz, 2H, OCH2), 2.25 (d, J=17.4Hz, 3H, CH3),1.11-0.97(m,3H,CH3).Enantiomeric
excess:>99%, determined by HPLC (Daicel Chirapak AD-H, hexane/isopropanol=80:
20, flow rate=0.8mL/min, λ=220nm):tR=9.255min (minor), tR=10.923min (major).
The chiral phosphoric acid catalyst for the asymmetry catalysis Biginelli reactions reported at present is mainly hand derived from dinaphthol
Property phosphoric acid ((a) J.Am.Chem.Soc., 2006,128,14802；(b) J.Am.Chem.Soc., 2009,131,15301), spiral shell
It is chiral single derived from chiral phosphoric acid catalyst derived from ring diphenol (Org.Biomol.Chem., 2012,10,4467) and TADDOL
Phosphoric acid (Advanced Synthesis＆Catalysis, 2005,347,1523), and chiral diphosphonic acid is urged derived from tartrate
There is not been reported for agent.So the application is by chirality 5,5,10,10- tetraphenyls two ring [4.4.0] -3,8- derived from tartrate
Bis phosphoric acid is used to be catalyzed the three component Biginelli reactions that benzaldehyde, ethyl acetoacetate and thiocarbamide are participated in, and investigates pair of reaction
Selectivity is reflected, is that ee values are weighed with enantiomeric excess, it is above-mentioned test result indicates that ee values are up to more than 99%, the mapping choosing of reaction
Selecting property is high, illustrates that the chiral induction ability of catalyst is very good.
Claims (3)
1. a kind of general structure isThe aryl of chiral 5,5,10,10- tetra-
The preparation method of two rings [4.4.0] -3,8- bis phosphoric acids, the Ar be phenyl, tolyl, chlorphenyl, bromophenyl, nitrobenzophenone or
Naphthyl, it is characterised in that the preparation method comprises the following steps：Optical pure tartaric acid ester and RMgBr are reacted,
Be made chirality 1, Isosorbide-5-Nitrae, the aryl erythrol of 4- tetra-, under organic base existence condition, by chirality 1, Isosorbide-5-Nitrae, the aryl erythrol of 4- tetra- with
High regioselectivity 1 occurs under the conditions of 0 DEG C -36 DEG C for POCl3, and chirality 5,5,10,10- is made in the reaction of 3- cycli phosphateizations
The ring of four aryl two [4.4.0] -3,8- bis phosphoric acids, described RMgBr formula be R in RMgBr, formula be phenyl, tolyl,
Chlorphenyl, bromophenyl, nitrobenzophenone or naphthyl；
The organic base is triethylamine or pyridine；
The mol ratio of the organic base and the aryl erythrol of chirality 1,1,4,4- tetra- is 10-30:1；
The concrete operation step of described high regioselectivity 1,3- cycli phosphateizations reaction is as follows：By the chiral benzene of 1,1,4,4- tetra-
Base erythrol is added in reaction vessel, and organic base is then added into reaction vessel, and reaction vessel is placed in into 0-10 DEG C of environment
In, after stirring 15 minutes, it is added dropwise under conditions of stirring into reaction vessel after POCl3, completion of dropping and continues to stir 30 points
Clock, is heated to 25-36 DEG C, after being further continued for stirring 120 minutes, with the pH value of 2mol/L hydrochloric acid regulation system to 1-2, after crystallization
Obtain chiral ring [4.4.0] -3,8- bis phosphoric acids of tetra- aryl of 5,5,10,10- two；
The mol ratio of the aryl erythrol of chiral 1,1,4,4- tetra- and POCl3 is 1:2-3.
2. preparation method according to claim 1, it is characterised in that：Described tartrate is ethyl tartrate or wine
Stone dimethyl phthalate.
3. preparation method according to claim 1, it is characterised in that：The mol ratio of tartrate and RMgBr is 1:6-
8。
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| 3,5-bis-O-(piperidinophosphoryl)-D-mannitol.《Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya》.1989,第426-32页. * |
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| Highly Enantioselective Biginelli Reaction Promoted by Chiral Bifunctional Primary Amine-Thiourea Catalysts: Asymmetric Synthesis of Dihydropyrimidines;Wang, Yangyun et al;《Advanced Synthesis & Catalysis》;20091231;第351卷(第18期);第3057-3062页 * |
| 手性1,1,4,4-四取代丁四醇的新化学;胡晓允;《中国博士学位论文全文数据库 工程科技I辑》;20150515(第5期);第2章，第6章 * |
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