CN105056991A

CN105056991A - Chiral phosphazene catalyst based on spiro framework adopting chiral diamine, preparation method and application of chiral phosphazene catalyst

Info

Publication number: CN105056991A
Application number: CN201510495960.4A
Authority: CN
Inventors: 韩建伟; 高省; 黄乃正
Original assignee: Shanghai Institute of Organic Chemistry of CAS
Current assignee: Shanghai Institute of Organic Chemistry of CAS
Priority date: 2015-08-13
Filing date: 2015-08-13
Publication date: 2015-11-18
Anticipated expiration: 2035-08-13
Also published as: CN105056991B

Abstract

The invention provides a chiral phosphazene catalyst based on a spiro framework adopting chiral diamine, a preparation method and an application of the chiral phosphazene catalyst. The catalyst has a structure represented in the general formula: (RX-)3P=NR', chiral groups are introduced through R and R', and the catalyst has a structure with two seven-membered rings in centered connection through phosphorspirol. Optically pure tartaric acid or substituted hexahydrophthalic acid or 1,2-cyclopentanedicarboxylicacid,(1R,2S)-rel- is taken as a raw material, chiral diamine is generated through esterification, a Grignard reaction, an optional chlorination reaction, an azido reaction and a reduction reaction of the raw material, then chiral diamine and phosphorus pentachloride have a spirocyclization reaction to construct a phosphorspirol-centered screw ring, the chiral phosphazene molecular catalyst is obtained under the alkaline condition, and a method for substituting azido for hydroxyl directly has good application and popularization value. The catalyst has the advantages of high catalysis efficiency, good stereoselectivity, mild conditions, economy, environmental protection, simplicity and convenience in operation and the like as well as popularization and application prospects.

Description

Based on the chiral phosphorus nitrile catalyst of the spirocyclic ring scaffold of chiral diamine, preparation method and application thereof

Technical field

The present invention relates to organic synthesis and field of catalytic chemistry.More particularly, the present invention relates to a kind of chiral phosphorus nitrile catalyst of the spirocyclic ring scaffold based on chiral diamine, preparation method and application thereof.The phosphonitrile micromolecular class super basic catalyst that system utilizes the adjacent dicarboxylic acids of chirality to be raw material preparation synthesis Luo Lin center, and the application of this catalyst in organic synthesis.The for example asymmetric cell reaction of the aryl oxidized indoles of 3-and dicarbonyl compound, comprise halogenation, hydroxylating, cyano group reacts, arylation reaction etc.

Background technology

Advanced medicine is the basis of hygiene and health.Because the underlying biological molecule of chirality phenomenon and vital movement is as protein, nucleic acid, polysaccharide etc. are closely bound up, so most is known and be chipal compounds at the advanced pharmaceutical molecules ground.According to statistics, the new drug of listing is over half is at present chiral drug.Asymmetry catalysis synthesis is then prepare one of chiral drug or the most efficient method of other chipal compounds, and its core develops outstanding chiral catalyst.The Nobel Prize three winners of calendar year 2001 get awards because exploitation has the contribution of the chiral catalyst of commercial Application potentiality.Since 2000, it is like a raging fire that organocatalysis field is developed; Design and prepare micromolecule catalyst and receive much concern.Up to now, existing various chiral acid base molecule, chiral pyridyl compounds, thiourea, triazole Cabbeen etc. is used as organic catalyst, and is widely used in asymmetric syntheses.Phosphonitrile compounds wherein containing-P=N-double bond is known super base molecule, the pK that phosphazene compound is combined with proton _bHvalue is close even more than 30.Therefore phosphorous volution organic molecule attract attention as super basic catalyst.Professor Maruoka of Kyoto Univ Japan has developed various two spiro quaternary ammonium salt based on dinaphthalene rigid backbone structure with quaternary alkylphosphonium salt phase transfer catalyst, wherein Maruoka also achieve the suitability for industrialized production (Shirakawa, the S. that catalyze and synthesize Non-natural chiral amino acid; Maruoka, K.Angew.Chem., Int.Ed.2013,52,2.); Professor Ooi develops the ion pair catalyst (IonPairCatalysts) of Luo Phosphonium ring, the phosphonitrile alkali catalyst of above-mentioned ion pair catalyst quaternary alkylphosphonium salt and inorganic base effect in-situ preparation-P=N-double bond, very high catalytic efficiency and selective (Uraguchi, D. is all achieved at multiple organic synthesis; Sakaki, S.; Ooi, T.J.Am.Chem.Soc.2007,129,12392; Uraguchi, D.; Ueki, Y.; Ooi, T.Science, 2009,326,120.).The asymmetric induction of chiral skeleton and control action are particularly important to the catalyst that design is outstanding, volution is as desirable chiral skeleton, its advantage is that structural rigidity is very strong, stable configuration, and therefore formed transition state intermediate is conducive to obtaining very high selective in asymmetric catalysis.Based on this, introduce a kind of rigidity and the very high chiral skeleton of stability of configuration is expected to prepare more outstanding catalyst; Although had hundreds of ripe chiral skeleton and outstanding catalyst thereof, the frame design synthesizing new catalyst based on autonomous property right has been still the focus in chiral catalysis research.

Based on this, the present invention, using the adjacent dicarboxylic acids of cheap chirality as raw material, has invented a large class pair volution phosphonitrile alkali catalyst, and using phosphorus as volution center, two heptatomic rings are with phosphorus center and carry multiple alkyl and aromatic group.

Compared with existing alkaline small catalyst, the catalyst that this patent relates to has following significant advantage:

1, strong alkali catalyst, catalytic efficiency is high;

2, outstanding stereoselectivity;

3, simple and easy to get, cost is low;

4, stablize air and steam, itself is not containing heavy metal, environmental protection;

5, catalyst can recycle after the reaction easily, thus significantly reduces reaction cost, substantially increases the practicality of chiral catalysis technology.

6, good substrate applicability, is easy to amplify.

Summary of the invention

The present invention relates to a class based on the chiral phosphorus nitrile catalyst of the spirocyclic ring scaffold of chiral diamine, preparation method and the application in asymmetry catalysis thereof; Using the adjacent dicarboxylic acids of the chirality of Threaric acid cheap and easy to get and replacement as raw material, through the linear synthesis of number step, obtain a series of pairs of volution super basic catalysts; Furtherly, this catalyst is a kind of chiral phosphorus nitrile catalyst of the spirocyclic ring scaffold based on chiral diamine, and containing multiple aromatic yl group or alkyl, two heptatomic rings form spiro phosphine center, have following molecular structural formula:

Wherein:

X＝NH。

R, R ' be selected from hydrogen, C ₁~ C ₂₀alkyl, C ₁~ C ₁₆perfluoroalkyl, C ₁~ C ₈containing fluoroalkyl replace aryl, C ₁~ C ₂₀the alkyl aryl, the aryl of halogen substiuted, the benzyl that the replace aryl, the C that replace ₁~ C ₄alkoxyl replace aryl, C ₆~ C ₁₂the aryl that replaces of aryl or containing the five-membered ring of O, N or S or the heteroaryl of hexatomic ring.

R, R ' prioritizing selection C ₁~ C ₄alkyl replace aryl, F, Cl or Br replace aryl, phenyl replace aryl; The five-membered ring of described O, N or S or the heteroaryl of hexatomic ring refer to pyridine radicals, thienyl or furan group.

In formula II, n=0,1 or 2; Preferably 1.

R ' substituting group can be selected from alone each position of hexatomic ring, and two heptatomic rings can be made to form C ₂symmetry.

Catalyst of the present invention has above-mentioned general formula Luo Lin center, and have-P=N-double bond to form a class super base molecule as basic group.

Catalyst of the present invention, shown in the following structural formula of preferred catalyst:

Wherein, described R, R ¹, R ²with described in claim 1.

In described catalyst, substituting group can be recommended further:

(1) when R is as fat group: R=H, methyl, ethyl, normal-butyl, benzyl, isopropyl, the tert-butyl group and chain alkyl are as cetyl, and long fluorocarbon chain, C ₈-C ₁₆perfluoroalkyl.

(2) when R is as aromatic group: R=Ar, shown in following chemical formula.

Catalyst of the present invention is sour based on the chiral tartaric be easy to get and the adjacent dicarboxylic acids of chirality is synthesis material, and according to the step of bibliographical information, through condensation reaction, esterification and grignard reaction synthesis obtain chiral diol.Then chiral diol obtains corresponding chiral diamine through azido reaction and reduction reaction; Then according to obtained chiral diol and chiral diamine, under the condition of phosphorus pentachloride or phosphorus pentabromide, there is the obtained quaternary alkylphosphonium salt of spirocyclization reaction, generate phosphonitrile super basic catalyst in the basic conditions, wherein have at least a reactive component to be chiral diamine.Be preferably two molecular chiral diamines and carry out spirocyclization reaction.

Method of the present invention, from chiral diol, is undertaken by following step (1) ~ (4).

(1) azido reaction: in organic solvent with at the temperature of-5 ~ 80 DEG C, under recommending 0 DEG C ~ room temperature, the reaction of chiral diol, sodium azide, trifluoroacetic acid and TFMS obtains product azide in 0.1 ~ 1 hour; The mol ratio 1: 2 ~ 5: 5 ~ 10: 10 ~ 20 of described chiral diol, sodium azide, trifluoroacetic acid and TFMS;

Add in organic solvents, chloroform by chiral diol, sodium azide, trifluoroacetic acid according to mol ratio, cooling, adds the mixed acid of TFMS and trifluoroacetic acid mol ratio 1: 1 ~ 1: 10.Stir, be warming up to room temperature, continue reaction 10 ~ 40 minutes.

Described azide is sodium azide, potassium azide or diphenyl phosphate azide.

This reaction with frozen water quencher reaction, can add ammonia neutralization to neutrality, separatory, extraction, washing, and dry, filter, concentrate and obtain crude product, recrystallization obtains solid product.

In described step (1), corresponding TFMS can utilize the concentrated sulfuric acid, and red fuming nitric acid (RFNA) and SPA substitute; Preferred TFMS.Azide can comprise sodium azide, potassium azide, and diphenyl phosphate azide (DPPA) etc. provides the reagent of nitrine.

Azido reaction of the present invention not only limits to the preparation for catalyst of the present invention.

(2) reduction reaction: product azide step (1) obtained, is dissolved in organic solvent, with Lithium Aluminium Hydride according to mol ratio 1: 4 ~ 1: 10, reacts 1 ~ 6 hour, quencher, filters, dry crude product at 0 DEG C; Again dissolve with ethyl acetate, saturated common salt water washing, dry, concentrate and obtain product, recrystallization obtains sterling.

Described step is in organic solvent in (2), and Lithium Aluminium Hydride also can utilize sodium borohydride etc. to go back original reagent and substitute.

(3) phosphonitrile salt precursor is prepared in spirocyclization reaction: in organic solvent with under reflux temperature, the tartaric acid skeleton that step (2) is obtained or the chiral diamine of cyclohexanediamine skeleton, with phosphorus pentachloride, triethylamine according to mol ratio 2: 1: 3 ~ 5: 1: 20, recommend 2: 1: 10; React 1 ~ 10 hour obtained quaternary alkylphosphonium salt.Cooling, filters, and quencher is reacted, concentrated, and recrystallization or column chromatography obtain solid product.

Phosphonitrile super basic catalyst is prepared in step (4) quaternization: be dissolved in organic solvent by the phosphonitrile salt precursor compound obtained in step (3), with in the tetrahydrofuran solution of monovalent metal hydroxide aqueous solution or potassium tert-butoxide and described phosphonitrile salt precursor compound be neutralized to neutrality; Then separatory, dry, concentrated, obtain crude product.Crude product recrystallization obtains product.

Described phosphonitrile salt precursor compound (Shou quaternary alkylphosphonium salt) and the mol ratio of monovalent metal hydroxide or potassium tert-butoxide are 1: 1 ~ 1: 20;

Described monovalent metal hydroxide is lithium hydroxide, NaOH or potassium hydroxide.

Described monovalent metal hydroxide aqueous solution is saturated aqueous solution.

Above-mentioned steps (1), (2), (3) or the organic solvent described in (4) can be chloroform, trichloroethanes, toluene, oxolane, benzinum, ether, carrene, or DMF equal solvent.

The chirality phosphonitrile base catalyst that the present invention relates to, not only can use as micromolecule catalyst separately, also can form metal complex catalyst as chiral ligand in conjunction with various transition metal and use.Above-mentioned catalyst application in the halogenation of active nucleophile, with almost quantitative yield be greater than the selective of 99%ee value and obtain corresponding halogenated products.Be applied to the Michael addition reaction of dicarbonyl compound, obtain almost quantitative yield and very outstanding stereoselectivity and enantioselectivity equally.Above-mentioned catalyst and palladium metal catalyst are as palladium bichloride, and palladium etc. carry out complexing, obtain chiral metal catalyst, also can obtain very outstanding yield and stereoselectivity at the allylation reaction of palladium chtalyst.

The nucleophile related in the present invention, comprises soft nucleophile to hard nucleophile, and wherein carbonyls comprises the derivative dicarbonyl compound of indone, 3-substituted indole ketones derivant etc.Shown in the following chemical formula of concrete necleophilic reaction:

Necleophilic reaction substrate:

Should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and can combining mutually between specifically described each technical characteristic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, tiredly no longer one by one to state at this.

Accompanying drawing explanation

Fig. 1 represents the X-ray single crystal diffraction structure chart of the phosphazene catalyst I-1 hydrochloride of embodiment 1.

Detailed description of the invention

The present inventor, through extensive and deep research, relates to synthesis and has prepared a series of volution phosphonitrile micromolecule catalyst, and utilized in asymmetric reaction.It is worthy of note, in preparation process, also found the direct azido reaction of vicinal diamines, this reaction has at medicine and materials industry applies extremely widely, therefore has huge application prospect.

Enantioselectivity

Term used herein " enantioselectivity " (enantioselectivity) refers to reaction, and preferential to generate in a pair enantiomter a certain, or a certain enantiomer in reaction preferential consumption enantiomter reactant (racemic modification), the latter is also called deracemization or asymmetric transformation.Enantiomer forms available term " enantiomeric excess (enantiomericexcess) " or " e.e.% " describes.It represents excessive to another enantiomer of enantiomer, usually represents with percentage.The numerical value related to herein carries out survey calculation gained by high performance liquid chromatography and high resolution gas chromatography and chiral chromatographic column; Computing formula is: e.e.%=(R-S)/(R+S) * 100%.

The major advantage of the catalyst that the present invention relates to:

1. strong alkali catalyst, catalytic efficiency is high; Catalytic amounts is low.

2. outstanding Stereo control, the enantioselectivity of reaction is high;

3. simple and easy to get, cost is low;

4. pair air and steam are stablized, and itself is not containing heavy metal, environmental protection;

5. reaction is amplified and is not significantly reduced enantioselectivity;

6. catalyst can recycle after the reaction easily, thus significantly reduces reaction cost, substantially increases the practicality of chiral catalysis technology.

7. good substrate applicability, is easy to amplify.

Be described in further detail the present invention below with reference to specific embodiment, but should be appreciated that, the present invention is not limited to these instantiations.In following examples, not marked specific experiment condition is usually according to usual operating conditions well known to those skilled in the art or the condition of advising according to manufacturer.Unless otherwise indicated, otherwise percentage is molar percentage.

Embodiment 1: the synthesis of phosphazene catalyst I-1

The first step: under an argon atmosphere, adds L-TARTARIC ACID (19.1g, 127mmol), absolute methanol (60mL) in reaction bulb; Be cooled to zero degree, slowly drip thionyl chloride (48.3mL, 665mmol), back flow reaction 3 hours.After reaction system cool to room temperature, take hydrogen chloride gas and unnecessary methyl alcohol away.With water (100mL) quencher, be extracted with ethyl acetate three (40mLX3), then anhydrous magnesium sulfate dryings; Filter, be spin-dried for, after vacuum drying, obtain micro-yellow oily liquid 2 (22.5g, 126mmol, 99%): ¹hNMR (300MHz, CDCl ₃): δ=4.52 (s, 2H), 3.79 (s, 6H), 3.67 (brs, 2H). ¹³cNMR (75MHz, CDCl ₃): δ=172.17,72.39,53.21.

Second step: dimethyl tartrate 2 (22.5g, 126mmol) is dissolved in 200mL carrene, adds a hydration p-methyl benzenesulfonic acid (12.0g, 63.0mmol) and 2,2-dimethoxypropane (101mL, 825mmol); Reaction backflow 4 hours, after reaction system cool to room temperature, is spin-dried for removal solvent, with water (100mL) cancellation reaction, is extracted with ethyl acetate three (40mLX3), then anhydrous magnesium sulfate dryings; Filter, be spin-dried for, after vacuum drying, obtain blush oily liquids 3 (24.1g, 124mmol, 98%): ¹hNMR (300MHz, CDCl ₃): δ=4.80 (s, 2H), 3.82 (s, 6H), 1.49 (s, 6H). ¹³cNMR (75MHz, CDCl ₃): δ=170.21,114.05,77.16,53.02,26.50.

3rd step: under an argon atmosphere, there-necked flask installs return channel, the dropping funel of band equilibrated valve, and a thermometer; Then fresh magnesium rod (14.1g, 579mmol, 1.02equiv.) and a fritter iodine is added as initator.Then in dropping funel, add the tetrahydrofuran solution (386mL) of bromobenzene (86.5g, 551mmol), slowly drip, until reaction starts.Constantly drop to complete, add hot reflux and continue reaction one hour, be then cooled to room temperature.

In above-mentioned grignard reagent, add dimethyl dimethyl tartrate 2 (24.1g, 124mmol), slowly add, ensure that temperature is no more than 20 degree, after being added dropwise to complete, reaction system adds hot reflux 1.5 hours, is then cooled to room temperature.Slowly add saturated ammonium chloride solution quencher reaction, be extracted with ethyl acetate three (40mLX3), then anhydrous magnesium sulfate dryings; Filter, be spin-dried for, after vacuum drying, obtain micro-yellow foamy solid; In carrene and methyl alcohol, recrystallization obtains white solid 4 (50.8g, 88%yield). ¹hNMR (300MHz, CDCl3): δ=7.57-7.50 (m, 4H), 7.39-7.22 (m, 16H), 4.59 (s, 2H), 4.03 (s, 2H), 1.04 (s, 6H). ¹³cNMR (75MHz, CDCl3): δ=146.23,142.85,129.08,128.36,128.07,127.79,127.52,109.64,81.11,78.38,27.41.HRMS (ESI) calculated value Calcd.forC ₃₁h ₃₄nO ₅ ⁺([M+NH ₄] ⁺) 484.2482, measured value found484.2483.

4th step: add TADDOL (4,5-bis-[hydroxyl (diphenyl) methyl]-2,2-dimethyl-1,3-dioxolane) 4 (7.7g, 16.6mol), chloroform 100mL in round-bottomed flask; Add thionyl chloride (3.6g, 60mmol), add backflow, then slowly drip the dichloromethane solution (100mL) of triethylamine (8.4g, 85mmol); Dropwise reaction two hours, with water (100mL) quencher, with dichloromethane extraction three times (40mLX3), saturated common salt water washing, then anhydrous magnesium sulfate drying; Filter, be spin-dried for, after vacuum drying, obtain white solid.In a round-bottomed flask, add sodium azide 4.32g (66.4mmol), DMF 33mL, ice bath is cooled to-5 DEG C-0 DEG C; Add 33mL trifluoroacetic acid and above-mentioned white solid; Be warming up to 80 degree, continue stirring reaction 24 hours, TLC detection reaction is complete, add trash ice, and be neutralized to neutrality gradually with 12-15% ammoniacal liquor, separatory, with dichloromethane extraction three times (40mLX3), saturated common salt water washing, then anhydrous magnesium sulfate drying; Filter, be spin-dried for, obtain white solid after vacuum drying, yield 82%. ¹HNMR(300MHz，CDCl ₃)：δ＝7.39-7.21(m，20H)，4.93(s，2H)，1.12(s，6H). ¹³CNMR(75MHz，CDCl ₃)：δ＝142.02，140.36，129.84，128.53，128.38，128.08，127.94，110.67，80.68，73.36，27.66。

Under an argon atmosphere, lithium aluminium hydride reduction (2.6g, 69.6mmol, 6.0equiv) and absolute ether (93mL) is added in there-necked flask; Above-mentioned oxolane (93mL) solution obtaining product azide (9.5g, 11.6mmol, 1.0equiv) slowly drips to there-necked flask, and dropwise, reaction system slowly returns to room temperature; Continue to stir, TLC detection reaction is complete, adds sodium sulphate saturated aqueous solution and destroys too much lithium aluminium hydride reduction, then filter, and washing, is spin-dried for.Use acetic acid ethyl dissolution crude product, saturated aqueous common salt repeatedly washs, then anhydrous magnesium sulfate drying; Filter, be spin-dried for, after vacuum drying, obtain white solid.Be recrystallized in n-hexane and ethyl acetate mixed solvent, obtain clear crystal (5), yield 97%. ¹HNMR(300MHz，CDCl ₃)：δ＝7.58-7.49(m，4H)，7.38-7.28(m，6H)，7.25-7.09(m，10H)，4.23(s，2H)，2.32(s，4H)，1.10(s，6H). ¹³CNMR(75MHz，CDCl ₃)：δ＝150.16，143.97，129.53，128.24，127.73，127.52，127.23，126.68，107.72，82.02，62.79，27.43.HRMS(ESI)：Calcd.forC ₃₁H ₃₃N ₂O ₂([M+H] ⁺)465.2532；found465.2537.

5th step: add TADDamine5 (4,5-bis-[amino (diphenyl) methyl]-2,2-dimethyl-1,3-dioxolanes in there-necked flask; 1.86g, 4.0mmol) and triethylamine (1.4mL, 10mmol), toluene 10mL, then slowly drips the toluene solution (10mL) of phosphorus pentachloride (0.42g, 2.0mmol), dropwise, be heated to 110 DEG C of reactions 2 hours.Reaction system returns to room temperature, crosses the triethylamine hydrochloride filtering generation, is spin-dried for and obtains crude product; Crude product is recrystallized in acetone and obtains catalyst precarsor (1.8g, 91%). and [α] _d ²⁷=-40.4 ° of (c=1.02, CHCl ₃). ¹hNMR (300MHz, CDCl ₃): δ=7.64 (d, J=7.7Hz, 8H), 7.31 (t, J=7.7Hz, 8H), 7.14 (dt, J=20.3,7.3Hz, 16H), 6.74 (d, J=7.5Hz, 8H), 4.85 (s, 4H), 1.88 (s, 4H), 0.65 (s, 12H). ¹³cNMR (75MHz, CDCl ₃): δ=145.35,145.23,142.20,142.17,130.23,128.70,128.38,128.31,127.61,127.19,109.39,81.30,66.57,26.63. ³¹pNMR (121MHz, CDCl ₃): δ=24.15.MS (MALDI): m/z (relativeintensity) ([M] ⁺) 954.9 (100), 955.9 (66), 957.0 (27), 958.0 (11), 959.0 (4) .HRMS (MALDI/DHB): Calcd.forC ₆₂h ₆₀n ₄o ₄p ^{+ 1}([M] ⁺) 955.4346; Found955.43467.IR (KBr): 3325,3058,3031,2989,2937,2740,1599,1494,1446,1416,1383,1248,1217,1165,1127,1065,969,876,752,696cm ^-1.

6th step: the catalyst precarsor in the 6th step is dissolved in tetrahydrofuran solution, slowly adds potassium hydroxide aqueous solution and be neutralized to neutrality, separatory, be spin-dried for tetrahydrofuran solution and obtain crude product, then obtain clear crystal by re-crystallizing in ethyl acetate; The phosphazene catalyst I-1 yield of this step almost quantitatively obtains.The X-ray single crystal diffraction structure of the hydrochloride of phosphazene catalyst I-1 is as illustrated shown in accompanying drawing 1.[α] _D ²⁷＝-62.0°(c＝1.02，CHCl ₃). ¹HNMR(300MHz，CDCl ₃)：δ＝7.27(m，40H)，5.37-4.47(m，4H)，3.33(brs，1H)，2.72(brs，2H)，0.76(d，J＝76.0Hz，12H). ¹³CNMR(75MHz，CDCl ₃)：δ＝147.70，143.66，130.17，128.22-127.0(m)，110.30，83.83，81.88，66.88，65.68，27.30. ³¹PNMR(121MHz，CDCl ₃)δ-6.81.MS(MALDI)：m/z(relativeintensity)([M+H] ⁺)954.7(100)，955.7(67)，956.7(20)，957.7(4).HRMS(MALDI/DHB)：Calcd.forC ₆₂H ₆₀N ₄O ₄P ⁺¹([M+H] ⁺)955.4340；found955.4347.IR(KBr)：3362，3057，3025，2987，2933，1599，1493，1446，1380，1305，1240，1218，1165，1055，1033，895，883，748，699cm ^-1.

Embodiment 2: the synthesis of phosphazene catalyst I-2

The first step: the synthetic method as I-1: under an argon atmosphere, adds L-TARTARIC ACID (19.1g, 127mmol), absolute methanol (60mL) in reaction bulb; Be cooled to zero degree, slowly drip thionyl chloride (48.3mL, 665mmol), back flow reaction 3 hours.After reaction system cool to room temperature, take hydrogen chloride gas and unnecessary methyl alcohol away.With water (100mL) quencher, be extracted with ethyl acetate three (40mLX3), then anhydrous magnesium sulfate dryings; Filter, be spin-dried for, after vacuum drying, obtain micro-yellow oily liquid 2 (22.5g, 126mmol, 99%): ¹hNMR (300MHz, CDCl ₃): δ=4.52 (s, 2H), 3.79 (s, 6H), 3.67 (brs, 2H). ¹³cNMR (75MHz, CDCl ₃): δ=172.17,72.39,53.21.

Second step: under an argon atmosphere, in there-necked flask, dimethyl tartrate 2 (9.8g, 126mmol) be dissolved in 150mL dimethoxy-ethane, be cooled to subzero 30 degree, add 1,1-dimethoxycyclohexane (5.3g, 37.0mmol), then drip the diethyl ether solution (5.45mL, 44mmol) of boron trifluoride; Remain on this thermotonus three hours, then reaction system is warmed up to room temperature.After reaction system is cooled to zero degree, with this reaction of the slow cancellation of the aqueous solution of saturated sodium bicarbonate.Be extracted with ethyl acetate three times (400mLX3), Separation of Organic layer, respectively wash once with 400mL water and saturated aqueous common salt.Then anhydrous magnesium sulfate drying is used; Filter, be spin-dried for, obtain oily liquids 6 after vacuum drying, purify (eluant, eluent: ethyl acetate/n-hexane=2/98-15/85) with column chromatography further, obtain colorless oil (8.07g, 31.23mmol, 85%). ¹HNMR(300MHz，CDCl ₃)：δ＝4.76(s，2H)，3.76(s，6H)，1.69-1.50(m，8H)，1.42-1.28(m，2H). ¹³CNMR(75MHz，CDCl ₃)：δ＝170.52，114.82，76.86，52.93，35.91，24.97，23.88.

3rd step: under an argon atmosphere, there-necked flask installs return channel, the dropping funel of band equilibrated valve, and a thermometer; Then fresh magnesium rod (14.1g is added, 579mmol, 1.02equiv.) He one fritter iodine is as initator. then in dropping funel, add bromobenzene (86.5g, tetrahydrofuran solution (386mL) 551mmol). then slowly drip, until reaction starts. dropwise, add hot reflux and continue reaction one hour, be then cooled to room temperature.

In above-mentioned grignard reagent, add cyclohexyl dimethyl tartrate 6 (32.0g, 124mmol), slowly add, ensure that temperature is no more than 20 degree, after being added dropwise to complete, reaction system adds hot reflux 1.5 hours, is then cooled to room temperature.Slowly add saturated aqueous ammonium chloride quencher reaction, be extracted with ethyl acetate three times (400mLX3), then anhydrous magnesium sulfate drying; Filter, be spin-dried for, after vacuum drying, obtain micro-yellow foamy solid; In carrene and methyl alcohol, recrystallization obtains white solid 7 (62g, 88%yield). ¹HNMR(300MHz，CDCl ₃)：δ＝7.55-7.48(m，4H)，7.41-7.22(m，16H)，4.55(s，2H)，3.98(s，2H)，1.50-1.33(m，4H)，1.30-1.09(m，6H). ¹³CNMR(75MHz，CDCl ₃)：δ＝146.35，142.90，128.84，128.34，127.94，127.76，127.40，110.16，80.65，78.48，70.85，36.74，26.71，25.28，24.20.HRMS(ESI)Calcd.forC ₃₄H ₃₈NO ₄ ⁺([M+NH ₄] ⁺)524.2795，found524.2796.

4th step: in 150mL round-bottomed flask, add chloroform 33mL, 4.32g (66.4mmol) sodium azide solid.Cooling, stirs, then in flask, adds 33mL trifluoroacetic acid, continues to stir 5-10 minute.Add chloroform (20mL) solution of the TADDOL derivative 7 that 8.3g (16.6mmol) cyclohexyl replaces.Then slowly TFA/20%TfOH solution is added carefully.Dropwise, continue stirring 30 minutes, then return to room temperature.TLC detection reaction is complete.Reactant liquor pours trash ice aqueous mixtures into, continues to stir, and then uses the ammonia neutralization of 12-15% to neutral.Divide liquid yield chloroform layer with separatory funnel, aqueous phase utilizes dichloromethane extraction (100mLX2), merges organic phase, washing, anhydrous sodium sulfate drying, and be spin-dried for removal solvent and obtain crude product, absolute ethyl alcohol recrystallization obtains white solid 7.5g, yield 81%. ¹HNMR(300MHz，CDCl ₃)：δ＝7.41-7.25(m，20H)，4.95(s，2H)，1.52-1.39(m，4H)，1.36-1.21(m，6H). ¹³CNMR(75MHz，CDCl ₃)：δ：＝142.34，140.53，129.86，128.61，128.41，128.03，127.90，127.85，111.08，80.23，73.41，36.98，25.23，24.39.HRMS(ESI)Calcd.forC ₃₄H ₃₂N ₆O ₂Na ⁺([M+Na] ⁺)579.2479，found579.2461。Under an argon atmosphere, lithium aluminium hydride reduction (2.6g, 69.6mmol, 6.0equiv) and absolute ether (93mL) is added in there-necked flask; THF (100mL) solution of the azide (6.4g, 11.6mmol) that previous step obtains slowly drips to there-necked flask, and dropwise, reaction system slowly returns to room temperature; Continue to stir, TLC detection reaction is complete.Add sodium sulphate saturated aqueous solution and destroy too much lithium aluminium hydride reduction, then filter, washing, is spin-dried for.Use acetic acid ethyl dissolution crude product, saturated aqueous common salt repeatedly washs, then anhydrous magnesium sulfate drying; Filter, be spin-dried for, after vacuum drying, obtain white solid (8).In n-hexane and ethyl acetate mixtures, recrystallization obtains clear crystal, yield 97%. ¹HNMR(300MHz，CDCl ₃)：δ＝7.62-7.51(m，4H)，7.39-7.28(m，6H)，7.27-7.13(m，10H)，4.22(s，2H)，2.38(s，4H)，1.46(d，J＝3.2Hz，4H)，1.30(d，J＝5.8Hz，6H). ¹³CNMR(75MHz，CDCl ₃)：δ＝150.40，144.10，129.57，128.22，127.89，127.48，127.24，127.18，126.65，108.03，81.66，63.01，36.85，25.49，24.26.HRMS(ESI)Calcd.forC ₃₄H ₃₇N ₂O ₂ ⁺([M+H] ⁺)505.2850，found505.2851.

5th step: add 8 (2.02g in there-necked flask, 4.0mmol) with triethylamine (1.4mL, 10mmol), toluene 10mL, then phosphorus pentachloride (0.42g is slowly dripped, toluene solution (10mL) 2.0mmol), dropwises, and is heated to 110 DEG C of reactions 2 hours.Reaction system returns to room temperature, crosses the triethylamine hydrochloride filtering generation, is spin-dried for and obtains crude product 9.

6th step: precursor 9 is directly dissolved in tetrahydrofuran solution, slowly add potassium hydroxide aqueous solution and be neutralized to neutrality, separatory, be spin-dried for tetrahydrofuran solution and obtain crude product I-2, then clear crystal 1.9g is obtained by re-crystallizing in ethyl acetate, two step overall yield 94%.[α] ³¹ _D＝-74.9°(c＝0.59，CHCl ₃). ¹HNMR(300MHz，CDCl ₃)：δ＝7.70-6.49(m，40H)，4.92(d，J＝61.6Hz，4H)，2.80(s，3H)，1.58-0.58(m，20H). ¹³CNMR(100MHz，CDCl ₃)：δ＝142.20，138.23，124.58，122.72，122.60，122.19，121.80，121.35，105.19，75.83，71.98，61.27，60.22，31.20，19.72，18.60. ³¹PNMR(121MHz，CDCl ₃)：δ＝-6.84(s).IR(KBr)：3361，3056，3027，2932，2858，1599，1493，1445，1365，1278，1165，1127，1099，1050，953，908，893，745，698，640cm ^-1.HRMS(MALDI/DHB)：CalcdforC ₆₂H ₆₀N ₄O ₄P ⁺([M+H] ⁺)1035.4973，found1035.4973.

Embodiment 3: the synthesis of phosphazene catalyst I-3

Second step: dimethyl tartrate 2 (22.5g, 126mmol) is dissolved in 200mL carrene, adds a hydration p-methyl benzenesulfonic acid (12.0g, 63.0mmol) and 2,2-dimethoxypropane (101mL, 825mmol); Reaction backflow 4 hours, after reaction system cool to room temperature, is spin-dried for removal solvent, with water (100mL) cancellation reaction, is extracted with ethyl acetate three times (40mLX3), then anhydrous magnesium sulfate drying; Filter, be spin-dried for, after vacuum drying, obtain blush oily liquids 3 (24.1g, 124mmol, 98%): ¹hNMR (300MHz, CDCl3): δ=4.80 (s, 2H), 3.82 (s, 6H), 1.49 (s, 6H). ¹³cNMR (75MHz, CDCl ₃): δ=170.21,114.05,77.16,53.02,26.50.

3rd step: under an argon atmosphere, there-necked flask installs return channel, the dropping funel of band equilibrated valve, and a thermometer; Then fresh magnesium rod (14.1g, 579mmol, 1.02equiv.) and a fritter iodine is added as initator.Then in dropping funel, para chlorobromobenzene (105g is added, tetrahydrofuran solution (386mL) 551mmol). slowly drip, until reaction starts. constantly drop to complete, add hot reflux and continue reaction one hour, be then cooled to room temperature.

In above-mentioned grignard reagent, add dimethyl dimethyl tartrate 2 (24.1g, 124mmol), slowly add, ensure that temperature is no more than 20 degree, after being added dropwise to complete, reaction system adds hot reflux 1.5 hours, is then cooled to room temperature.Slowly add saturated ammonium chloride solution quencher reaction, be extracted with ethyl acetate three (40mLX3), then anhydrous magnesium sulfate dryings; Filter, be spin-dried for, after vacuum drying, obtain micro-yellow foamy solid; In carrene and methyl alcohol, recrystallization obtains white solid 10 (56g, 75% yield). ¹HNMR(300MHz，CDCl ₃)：δ＝7.40(d，J＝8.0Hz，4H)，7.32(d，J＝7.9Hz，4H)，7.20(s，8H)，5.03(s，2H)，4.39(s，2H)，1.09(s，6H). ¹³CNMR(75MHz，CDCl ₃)：δ＝143.62，140.72，134.02，133.91，130.11，129.24，128.64，127.91，110.09，80.79，77.79，27.44.

4th step: in 150mL round-bottomed flask, add chloroform 33mL, 4.32g (66.4mmol) sodium azide solid.Cooling, stirs, then in flask, adds 33mL trifluoroacetic acid, continues to stir 5-10 minute.Add chloroform (20mL) solution of 10 (10g, 16.6mol).Then slowly TFA/20%TfOH solution is added carefully.Dropwise, continue stirring 30 minutes, then return to room temperature.TLC detection reaction is complete.Reactant liquor pours trash ice aqueous mixtures into, continues to stir, and then uses the ammonia neutralization of 12-15% to neutral.Divide liquid yield chloroform layer with separatory funnel, aqueous phase utilizes dichloromethane extraction (100mLX2), merges organic phase, washing, anhydrous sodium sulfate drying, is spin-dried for removal solvent and obtains crude product, 8.2g, yield 76%.[α] ²⁹ _D＝-34.7°(c＝0.54，CHCl ₃). ¹HNMR(300MHz，CDCl ₃)：δ＝7.39-7.12(m，16H)，4.81(s，2H)，1.22(s，6H). ¹³CNMR(75MHz，CDCl ₃)：δ＝139.95，138.45，134.44，134.30，130.97，129.72，128.72，128.40，111.01，80.57，72.37，27.67.IR(KBr)：2978，2895，2105，1592，1491，1400，1371，1262，1236，1209，1167，1095，1076，1014，978，915，878，840，819，774，739，672，535，519cm ^-1.HRMS(ESI)Calcd.forC ₃₁H ₂₅Cl ₄N ₄O ₂ ⁺([M-N ₂+H] ⁺)625.0726.found625.0676.

Under an argon atmosphere, lithium aluminium hydride reduction (2.6g, 69.6mmol, 6.0equiv) and anhydrous tetrahydro furan (93mL) is added in there-necked flask; THF (93mL) solution of azide (7.6g, 11.6mmol, 1.0equiv) slowly drips to there-necked flask, and dropwise, reaction system slowly returns to room temperature; Continue to stir, TLC detection reaction is complete, adds sodium sulphate saturated aqueous solution and destroys too much lithium aluminium hydride reduction, then filter, and washing, is spin-dried for.Use acetic acid ethyl dissolution crude product, saturated aqueous common salt repeatedly washs, then anhydrous magnesium sulfate drying; Filter, be spin-dried for, after vacuum drying, obtain white solid (11).Be recrystallized in n-hexane and ethyl acetate mixed solvent, obtain clear crystal, yield 96%. [α] ³¹ _d=-50.3 ° of (c=0.51, CHCl ₃). ¹hNMR (300MHz, CDCl ₃): δ=7.48 (d, J=8.4Hz, 4H), 7.34 (d, J=8.5Hz, 4H), 7.17 (d, J=8.5Hz, 4H), 7.03 (d, J=8.4Hz, 4H), 4.11 (s, 2H), 2.33 (s, 4H), 1.14 (s, 6H). ¹³cNMR (75MHz, CDCl ₃): δ=147.92,141.92,133.54,132.71,130.76,129.02,128.48,127.90,108.03,81.77,62.21,27.43.IR (KBr): 3362,3251,3163,2983,2932,2878,1589,1489,1399,1379,1370,1236,1170,1094,1066,1013,892,819,767,699,518cm ^-1.HRMS (ESI) Calcd.forC ₃₁h ₂₉cl ₄n ₂o ₂ ⁺([M+H] ⁺) 601.0978, found601.0977.

5th step: add TADDamine11 (2.4g in there-necked flask, 4.0mmol) with triethylamine (1.4mL, 10mmol), toluene 10mL, then phosphorus pentachloride (0.42g is slowly dripped, toluene solution (10mL) 2.0mmol), dropwises, and is heated to 110 DEG C of reactions 2 hours.Reaction system returns to room temperature, crosses the triethylamine hydrochloride filtering generation, is spin-dried for and obtains crude product; Crude product is recrystallized in acetone and obtains catalyst precarsor 12, without the need to being further purified, directly carries out next step reaction.

6th step: be directly dissolved in tetrahydrofuran solution by the compound obtained in the 5th step, slowly add potassium hydroxide aqueous solution and be neutralized to neutrality, separatory, be spin-dried for tetrahydrofuran solution and obtain crude product, then obtains clear crystal I-3 by re-crystallizing in ethyl acetate; The overall yield of two steps is 87% (2.1g).[α] ³¹ _D＝-79.8°(c＝0.52，CHCl ₃). ¹HNMR(300MHz，CDCl ₃)：δ＝7.59-6.76(m，32H)，4.91(brs，4H)，3.34(brs，1H)，2.55(brs，2H)，0.78(d，J＝65.5Hz，12H). ¹³CNMR(100MHz，CDCl ₃)：δ＝145.05，141.15，133.48，130.77，128.66，128.48，127.60，110.66，81.08，77.26，66.20，64.67，26.89. ³¹PNMR(121MHz，CDCl ₃)：δ＝-7.52(s).IR(KBr)：3366，3057，2986，2933，1591，1573，1490，1399，1381，1242，1219，1164，1096，1013，906，888，837，815，776，733，719，700，541，528cm ^-1.HRMS(MALDI/DHB)：CalcdforC ₆₂H ₅₂N ₄O ₄Cl ₈P ⁺([M+H] ⁺)1227.1229，found1227.1220.

Embodiment 4: the synthesis of phosphazene catalyst I-4

3rd step: under an argon atmosphere, there-necked flask installs return channel, the dropping funel of band equilibrated valve, and a thermometer; Then fresh magnesium rod (14.1g, 579mmol, 1.02equiv.) and a fritter iodine is added as initator.Then add tert-butyl group bromobenzene (117g in dropping funel, tetrahydrofuran solution (386mL) 551mmol). slowly drip, until reaction starts. constantly drop to complete, add hot reflux and continue reaction one hour, be then cooled to room temperature.

In above-mentioned grignard reagent, add dimethyl dimethyl tartrate 2 (24.1g, 124mmol), slowly add, ensure that temperature is no more than 20 degree, after being added dropwise to complete, reaction system adds hot reflux 1.5 hours, is then cooled to room temperature.Slowly add saturated ammonium chloride solution quencher reaction, be extracted with ethyl acetate three (40mLX3), then anhydrous magnesium sulfate dryings; Filter, be spin-dried for, after vacuum drying, obtain micro-yellow foamy solid; In carrene and methyl alcohol, recrystallization obtains white solid 13 (69g, 79% yield). ¹HNMR(300MHz，CDCl ₃)：δ＝7.46(d，J＝8.4Hz，4H)，7.33(d，J＝8.4Hz，4H)，7.28(s，8H)，4.56(s，2H)，4.26(s，2H)，1.34(s，18H)，1.28(s，18H)，1.01(s，6H). ¹³CNMR(75MHz，CDCl ₃)：δ＝150.06，149.95，143.56，139.91，128.66，127.67，125.15，124.29，109.46，81.38，78.04，34.76，34.69，31.81，31.65，27.33.HRMS(ESI)Calcd.forC ₄₇H ₆₆NO ₄ ⁺([M+NH ₄] ⁺)708.4986，found708.4985.

4th step: in 150mL round-bottomed flask, add chloroform 33mL, 4.32g (66.4mmol) sodium azide solid.Cooling, stirs, then in flask, adds 33mL trifluoroacetic acid, continues to stir 5-10 minute.Add chloroform (20mL) solution of 13 (11.7g, 16.6mol).Then slowly TFA/20%TfOH solution is added carefully.Dropwise, continue stirring 30 minutes, then return to room temperature.TLC detection reaction is complete.Reactant liquor pours trash ice aqueous mixtures into, continues to stir, and then uses the ammonia neutralization of 12-15% to neutral.Divide liquid yield chloroform layer with separatory funnel, aqueous phase utilizes dichloromethane extraction (100mLX2), merges organic phase, washing, anhydrous sodium sulfate drying, is spin-dried for remove solvent to obtain crude product be white solid (11.5g, yield 91%).[α] ³⁰ _D＝-48.2°(c＝0.50，CHCl ₃). ¹HNMR(300MHz，CDCl ₃)：δ＝7.37-7.29(m，8H)，7.28-7.19(m，8H)，4.98(s，2H)，1.31(d，J＝10.8Hz，36H)，1.01(s，6H). ¹³CNMR(75MHz，CDCl ₃)：δ＝150.67，150.43，139.26，137.56，129.66，128.26，125.18，124.71，110.94，80.93，73.34，34.79，31.67，31.58，27.72.IR(KBr)：3035，2963，2904，2868，2107，1509，1461，1364，1269，1217，1166，1110，1070，1018，977，931，879，827，775，718，582，571cm ^-1.HRMS(ESI)Calcd.forC ₄₇H ₆₀N ₆O ₂Na ⁺([M+Na] ⁺)763.4670，founr763.4656.

Under an argon atmosphere, lithium aluminium hydride reduction (2.6g, 69.6mmol, 6.0equiv) and anhydrous tetrahydro furan (93mL) is added in there-necked flask; THF (93mL) solution of the azide (8.8g, 11.6mmol, 1.0equiv) obtained slowly drips to there-necked flask, and dropwise, reaction system slowly returns to room temperature; Continue to stir, TLC detection reaction is complete, adds sodium sulphate saturated aqueous solution and destroys too much lithium aluminium hydride reduction, then filter, and washing, is spin-dried for.Use acetic acid ethyl dissolution crude product, saturated aqueous common salt repeatedly washs, then anhydrous magnesium sulfate drying; Filter, be spin-dried for, after vacuum drying, obtain white solid (14).Be recrystallized in n-hexane and ethyl acetate mixed solvent, obtain clear crystal 7.7g, yield 97%. [α] ³¹ _d=+41.5 ° of (c=0.93, CHCl ₃). ¹hNMR (300MHz, CDCl ₃): δ=7.52 (d, J=8.3Hz, 4H), 7.39 (d, J=8.3Hz, 4H), 7.29 (d, J=8.3Hz, 4H), 7.16 (d, J=8.3Hz, 4H), 4.35 (s, 2H), 2.38 (s, 4H), 1.42 (s, 18H), 1.34 (s, 18H), 1.15 (s, 6H). ¹³cNMR (75MHz, CDCl ₃): δ=149.35,148.68,147.34,140.91,128.88,127.07,124.79,123.95,107.29,81.84,62.02,34.44,34.31,31.52,31.40,27.14.IR (KBr): 3089,3033,2963,2903,2867,1585,1509,1475,1461,1403,1377,1363,1269,1237,1214,1171,1110,1065,1017,894,839,823,772,703,600,583cm ^-1.HRMS (ESI) Calcd.forC ₄₇h ₆₅n ₂o ₂ ⁺([M+H] ⁺) 689.5041, found689.5039.

5th step: add TADDamine14 (2.7g in there-necked flask, 4.0mmol) with triethylamine (1.4mL, 10mmol), toluene 10mL, then phosphorus pentachloride (0.42g is slowly dripped, toluene solution (10mL) 2.0mmol), dropwises, and is heated to 110 DEG C of reactions 2 hours.Reaction system returns to room temperature, crosses the triethylamine hydrochloride filtering generation, is spin-dried for and obtains crude product; Crude product is recrystallized in acetone and obtains catalyst precarsor, without the need to being further purified, directly carries out next step reaction.

6th step: the compound obtained in the 5th step is directly dissolved in tetrahydrofuran solution, slowly add potassium hydroxide aqueous solution and be neutralized to neutrality, separatory, is spin-dried for tetrahydrofuran solution and obtains catalyst crude product I-4, then obtain clear crystal 2.6g by re-crystallizing in ethyl acetate; The overall yield of two steps is 93%.[α] ³² _D＝-103.1°(c＝0.58，CHCl ₃). ¹HNMR(300MHz，CDCl ₃)：δ＝7.53-7.10(m，28H)，6.90(d，J＝6.0Hz，4H)，5.06(d，J＝35.8Hz，4H)，3.13(s，3H)，1.42(s，36H)，1.17(d，J＝17.0Hz，36H)，0.88(d，J＝32.4Hz，12H). ¹³CNMR(100MHz，CDCl ₃)：δ＝149.36，149.15，148.14，145.03，140.48，129.72，129.14，127.69，126.98，124.77，124.13，124.01，109.31，83.38，82.94，77.27，64.88，64.55，34.47，34.44，34.24，34.17，31.72，31.59，31.26，27.09，26.85. ³¹PNMR(121MHz，CDCl ₃)：δ＝-4.52(s).IR(KBr)：3362，3032，2963，2903，2868，1508，1462，1393，1378，1364，1269，1242，1218，1167，1108，1057，1017，891，841，823，783，713，574cm ^-1.HRMS(MALDI/DHB)：CalcdforC ₉₄H ₁₂₄N ₄O ₄P ⁺([M+H] ⁺)1403.9355，found1403.9341.

Embodiment 5: the synthesis of phosphazene catalyst I-5

Second step: dimethyl tartrate 2 (22.5g, 126mmol) is dissolved in 200mL carrene, adds a hydration p-methyl benzenesulfonic acid (12.0g, 63.0mmol) and 2,2-dimethoxypropane (101mL, 825mmol); Reaction backflow 4 hours, after reaction system cool to room temperature, is spin-dried for removal solvent, with water (100mL) cancellation reaction, is extracted with ethyl acetate three (40mLX3), then anhydrous magnesium sulfate dryings; Filter, be spin-dried for, after vacuum drying, obtain blush oily liquids 3 (24.1g, 124mmol, 98%): ¹hNMR (300MHz, CDCl3): δ=4.80 (s, 2H), 3.82 (s, 6H), 1.49 (s, 6H). ¹³cNMR (75MHz, CDCl ₃): δ=170.21,114.05,77.16,53.02,26.50.

3rd step: under an argon atmosphere, there-necked flask installs return channel, the dropping funel of band equilibrated valve, and a thermometer; Then fresh magnesium rod (14.1g, 579mmol, 1.02equiv.) and a fritter iodine is added as initator.Then add phenyl bromobenzene (127g in dropping funel, tetrahydrofuran solution (386mL) 551mmol). slowly drip, until reaction starts. constantly drop to complete, add hot reflux and continue reaction one hour, be then cooled to room temperature.

In above-mentioned grignard reagent, add dimethyl dimethyl tartrate 2 (24.1g, 124mmol), slowly add, ensure that temperature is no more than 20 degree, after being added dropwise to complete, reaction system adds hot reflux 1.5 hours, is then cooled to room temperature.Slowly add saturated ammonium chloride solution quencher reaction, be extracted with ethyl acetate three (40mLX3), then anhydrous magnesium sulfate dryings; Filter, be spin-dried for, after vacuum drying, obtain micro-yellow foamy solid; In carrene and methyl alcohol, recrystallization obtains white solid 15 (83g, 87% yield). ¹HNMR(300MHz，CDCl ₃)：δ＝7.74-7.61(m，12H)，7.60-7.31(m，24H)，4.77(s，2H)，4.39(s，2H)，1.21(s，6H). ¹³CNMR(75MHz，CDCl ₃)：δ＝144.58，141.74，140.59，140.57，140.30，139.89，128.98，128.77，128.71，128.02，127.30，127.27，127.03，127.02，126.86，125.98，109.73，81.06，78.06，27.31.HRMS(ESI)Calcd.forC ₅₅H ₄₅O ₄ ^-([M-H] ^-)769.3318，found769.3345.

4th step: in 150mL round-bottomed flask, add chloroform 33mL, 4.32g (66.4mmol) sodium azide solid.Cooling, stirs, then in flask, adds 33mL trifluoroacetic acid, continues to stir 5-10 minute.Add chloroform (20mL) solution of 15 (12.7g, 16.6mol).Then slowly TFA/20%TfOH solution is added carefully.Dropwise, continue stirring 30 minutes, then return to room temperature.TLC detection reaction is complete.Reactant liquor pours trash ice aqueous mixtures into, continues to stir, and then uses the ammonia neutralization of 12-15% to neutral.Divide liquid yield chloroform layer with separatory funnel, aqueous phase utilizes dichloromethane extraction (100mLX2), merges organic phase, washing, anhydrous sodium sulfate drying, is spin-dried for removal solvent and obtains white solid (10.3g, 75%). ¹hNMR (300MHz, CDCl ₃): δ=7.69-7.52 (m, 16H), 7.51-7.29 (m, 20H), 5.08 (s, 2H), 1.25 (s, 6H). ¹³cNMR (75MHz, CDCl ₃): δ=140.97,140.72,140.58,139.51,130.30,129.12,129.07,128.96,127.83,127.71,127.36,127.10,126.66,111.05,81.05,73.33,27.87.HRMS (ESI) Calcd.forC ₅₅h ₄₄n ₆o ₂na ⁺([M+Na] ⁺) 843.3423, found843.3467.

Under an argon atmosphere, lithium aluminium hydride reduction (2.6g, 69.6mmol, 6.0equiv) and anhydrous tetrahydro furan (93mL) is added in there-necked flask; THF (93mL) solution of product azide (8.9g, 11.6mmol, 1.0equiv) slowly drips to there-necked flask, and dropwise, reaction system slowly returns to room temperature; Continue to stir, TLC detection reaction is complete, adds sodium sulphate saturated aqueous solution and destroys too much lithium aluminium hydride reduction, then filter, and washing, is spin-dried for.Use acetic acid ethyl dissolution crude product, saturated aqueous common salt repeatedly washs, then anhydrous magnesium sulfate drying; Filter, be spin-dried for, after vacuum drying, obtain white solid (16).Be recrystallized in n-hexane and ethyl acetate mixed solvent, obtain clear crystal 8.8g, yield 99%. [α] ³¹ _d=-60.3 ° of (c=0.51, CHCl ₃). ¹hNMR (300MHz, CDCl ₃): δ=7.78-7.67 (m, 12H), 7.61-7.29 (m, 24H), 4.45 (s, 2H), 2.45 (s, 4H), 1.26 (s, 6H). ¹³cNMR (75MHz, CDCl ₃): δ=149.19,143.17,140.98,139.82,139.50,129.99,129.12,129.01,128.17,127.63,127.29,127.06,126.21,108.00,82.18,62.69,27.59.HRMS (ESI) Calcd.forC ₅₅h ₄₉n ₂o ₂ ⁺([M+H] ⁺) 769.3789, found769.3785.

5th step: add TADDamine16 (3.1g in there-necked flask, 4.0mmol) with triethylamine (1.4mL, 10mmol), toluene 10mL, then phosphorus pentachloride (0.42g is slowly dripped, toluene solution (10mL) 2.0mmol), dropwises, and is heated to 110 DEG C of reactions 2 hours.Reaction system returns to room temperature, crosses the triethylamine hydrochloride filtering generation, is spin-dried for and obtains crude product; Crude product is recrystallized in acetone and obtains catalyst precarsor, without the need to being further purified, directly carries out next step reaction.

6th step: be directly dissolved in tetrahydrofuran solution by the compound obtained in the 5th step, slowly add potassium hydroxide aqueous solution and be neutralized to neutrality, separatory, be spin-dried for tetrahydrofuran solution and obtain crude product, then obtains clear crystal I-52.9g by re-crystallizing in ethyl acetate; The overall yield of two steps is 95%.[α] ³¹ _D＝-82.0°(c＝0.60，CHCl ₃). ¹HNMR(300MHz，CDCl ₃)：δ＝8.01-6.96(m，72H)，5.15(d，J＝12.2Hz，4H)，3.25(s，3H)，0.92(d，J＝36.6Hz，12H). ¹³CNMR(100MHz，CDCl ₃)：δ＝141.57，137.67，135.34，135.01，134.23，133.83，125.17，123.57，122.85，122.06，121.93，121.77，121.64，121.30，120.87，104.89，77.59，72.11，60.70，22.00. ³¹PNMR(121MHz，CDCl ₃)：δ＝-6.05.IR(KBr)：3361，3054，3027，2984，2931，1599，1485，1402，1379，1242，1216，1164，1058，1007，907，889，828，762，744，695，638，567，510cm ^-1.HRMS(MALDI/DHB)：CalcdforC ₁₁₀H ₉₂N ₄O ₄P ⁺([M+H] ⁺)1563.6851，found1563.6842.

Embodiment 6: the synthesis of phosphazene catalyst I-6

Second step: dimethyl tartrate 2 (22.5g, 126mmol) is dissolved in 200mL carrene, adds a hydration p-methyl benzenesulfonic acid (12.0g, 63.0mmol) and 2,2-dimethoxypropane (101mL, 825mmol); Reaction backflow 4 hours, after reaction system cool to room temperature, is spin-dried for removal solvent, with water (100mL) cancellation reaction, is extracted with ethyl acetate three times (40mLX3), then anhydrous magnesium sulfate drying; Filter, be spin-dried for, after vacuum drying, obtain blush oily liquids 3 (24.1g, 124mmol, 98%): ¹hNMR (300MHz, CDCl ₃): δ=4.80 (s, 2H), 3.82 (s, 6H), 1.49 (s, 6H). ¹³cNMR (75MHz, CDCl ₃): δ=170.21,114.05,77.16.53.02,26.50.

3rd step: under an argon atmosphere, there-necked flask installs return channel, the dropping funel of band equilibrated valve, and a thermometer; Then fresh magnesium rod (14.1g, 579mmol, 1.02equiv.) and a fritter iodine is added as initator.Then in dropping funel, 3 are added, the tetrahydrofuran solution (386mL) of 5-dimethyl bromobenzene (101g, 551mmol). slowly drip, until reaction starts. constantly drop to complete, add hot reflux and continue reaction one hour, be then cooled to room temperature.

In above-mentioned grignard reagent, add dimethyl dimethyl tartrate 2 (24.1g, 124mmol), slowly add, ensure that temperature is no more than 20 degree, after being added dropwise to complete, reaction system adds hot reflux 1.5 hours, is then cooled to room temperature.Slowly add saturated ammonium chloride solution quencher reaction, be extracted with ethyl acetate three times (40mLX3), then anhydrous magnesium sulfate drying; Filter, be spin-dried for, after vacuum drying, obtain micro-yellow foamy solid; In carrene and methyl alcohol, recrystallization obtains white solid 17 (58g, 81% yield). ¹HNMR(300MHz，CDCl ₃)：δ＝7.18(s，4H)，6.97(s，6H)，6.88(s，2H)，4.58(s，2H)，3.86(s，2H)，2.34(s，12H)，2.26(s，12H)，1.09(s，6H). ¹³CNMR(75MHz，CDCl ₃)：δ＝146.30，142.90，137.52，136.57，129.38，128.94，126.74(d，J＝3.8Hz)，125.71(d，J＝4.1Hz)，109.41，81.37，78.11，27.35，21.83(d，J＝1.3Hz).HRMS(ESI)Calcd.forC ₃₉H ₅₀NO ₄ ⁺([M+NH ₄] ⁺)596.3734，found596.3733.

4th step: in 150mL round-bottomed flask, add chloroform 33mL, 4.32g (66.4mmol) sodium azide solid.Cooling, stirs, then in flask, adds 33mL trifluoroacetic acid, continues to stir 5-10 minute.Add chloroform (20mL) solution of 17 (9.6g, 16.6mol).Then slowly TFA/20%TfOH solution is added carefully.Dropwise, continue stirring 30 minutes, then return to room temperature.TLC detection reaction is complete.Reactant liquor pours trash ice aqueous mixtures into, continues to stir, and then uses the ammonia neutralization of 12-15% to neutral.Divide liquid yield chloroform layer with separatory funnel, aqueous phase utilizes dichloromethane extraction (100mLX2), merges organic phase, washing, anhydrous sodium sulfate drying, is spin-dried for removal solvent and obtains white solid (9.3g, yield 89%). and [α] ³⁰ _d=+3.0 ° of (c=0.52, CHCl ₃). ¹hNMR (300MHz, CDCl ₃): δ=6.94 (s, 6H), 6.89 (s, 6H), 4.85 (s, 2H), 2.30 (d, J=3.9Hz, 24H), 1.19 (s, 6H). ¹³cNMR (75MHz, CDCl ₃): δ=142.00,140.39,137.50,137.01,129.64,129.49,127.42,126.17,109.83,80.81,73.28,27.49,21.92,21.85.IR (KBr): 2985,2916,2865,2108,1600,1461,1451,1379,1369,1239,1167,1073,1038,891,849,770,737cm ^-1.HRMS (ESI) Calcd.forC ₃₉h ₄₄n ₆o ₂na ⁺([M+Na] ⁺) 651.3423, found651.3421.

Under an argon atmosphere, lithium aluminium hydride reduction (2.6g, 69.6mmol, 6.0equiv) and anhydrous tetrahydro furan (93mL) is added in there-necked flask; THF (93mL) solution of azide (7.3g, 11.6mmol, 1.0equiv) slowly drips to there-necked flask, and dropwise, reaction system slowly returns to room temperature; Continue to stir, TLC detection reaction is complete, adds sodium sulphate saturated aqueous solution and destroys too much lithium aluminium hydride reduction, then filter, and washing, is spin-dried for.Use acetic acid ethyl dissolution crude product, saturated aqueous common salt repeatedly washs, then anhydrous magnesium sulfate drying; Filter, be spin-dried for, after vacuum drying, obtain white solid (18).Be recrystallized in n-hexane and ethyl acetate mixed solvent, obtain clear crystal 6.5g, yield 97%yield. [α] ³¹ _d=-43.5 ° of (c=0.53, CHCl ₃). ¹hNMR (300MHz, CDCl ₃): δ=7.14 (s, 4H), 6.95 (s, 2H), 6.80 (d, J=9.5Hz, 6H), 4.22 (s, 2H), 2.32 (s, 12H), 2.23 (s, 12H), 2.10 (s, 4H), 1.18 (s, 6H). ¹³cNMR (75MHz, CDCl ₃): δ=149.97,144.10,137.48,136.56,128.59,128.46,127.14,125.59,107.32,82.29,62.35,27.35,21.90.IR (KBr): 3363,3252,3164,3002,2981,2914,2864,1599,1454,1376,1367,1236,1168,1070,893,848,747,714,689cm ^-1.HRMS (ESI) Calcd.forC ₃₉h ₄₉n ₂o ₂ ⁺([M+H] ⁺) 577.3789, found577.37890.

5th step: add TADDamine18 (2.3g in there-necked flask, 4.0mmol) with triethylamine (1.4mL, 10mmol), toluene 10mL, then phosphorus pentachloride (0.42g is slowly dripped, toluene solution (10mL) 2.0mmol), dropwises, and is heated to 110 DEG C of reactions 2 hours.Reaction system returns to room temperature, crosses the triethylamine hydrochloride filtering generation, is spin-dried for and obtains crude product; Crude product is recrystallized in acetone and obtains catalyst precarsor, without the need to being further purified, directly carries out next step reaction.

6th step: be directly dissolved in tetrahydrofuran solution by the compound obtained in the 5th step, slowly add potassium hydroxide aqueous solution and be neutralized to neutrality, separatory, is spin-dried for the crude product that tetrahydrofuran solvent obtains I-6, then obtains clear crystal by re-crystallizing in ethyl acetate; The overall yield of two steps is 91% (2.1g).[α] ³² _D＝-70.1°(c＝0.64，CHCl ₃). ¹HNMR(300MHz，CDCl ₃)：δ＝8.42-6.08(m，24H)，4.93(s，4H)，3.46(d，J＝101.6Hz，3H)，2.25(s，48H)，1.62-0.21(m，12H). ¹³CNMR(100MHz，CDCl ₃)：δ＝154.07，148.70，147.55，146.22，143.13，141.75，136.93，136.55，135.49，129.59，128.43，128.16，126.85，125.19，111.15，107.66，84.11，80.44，77.30，67.89，66.34，64.29，27.81，27.76，26.59，26.16，21.77，21.62，21.56. ³¹PNMR(121MHz，CDCl ₃)：δ＝-12.07(s).IR(KBr)：3350，2984，2916，2863，1599，1455，1377，1239，1216，1168，1065，954，929，909，888，850，766，757，736，693cm ^-1.HRMS(MALDI/DHB)：CalcdforC ₇₈H ₉₂N ₄O ₄P ⁺([M+H] ⁺)1179.6851，found1179.6847.

Embodiment 7: the synthesis of phosphazene catalyst I-7

3rd step: under an argon atmosphere, there-necked flask installs return channel, the dropping funel of band equilibrated valve, and a thermometer; Then fresh magnesium rod (14.1g, 579mmol, 1.02equiv.) and a fritter iodine is added as initator.Then in dropping funel, add 4-methyl bromobenzene (94.2g, tetrahydrofuran solution (386mL) 551mmol). slowly drip, until reaction starts. constantly drop to complete, add hot reflux and continue reaction one hour, be then cooled to room temperature.

In above-mentioned grignard reagent, add dimethyl dimethyl tartrate 2 (24.1g, 124mmol), slowly add, ensure that temperature is no more than 20 degree, after being added dropwise to complete, reaction system adds hot reflux 1.5 hours, is then cooled to room temperature.Slowly add saturated ammonium chloride solution quencher reaction, be extracted with ethyl acetate three times (40mLX3), then anhydrous magnesium sulfate drying; Filter, be spin-dried for, after vacuum drying, obtain micro-yellow foamy solid; In carrene and methyl alcohol, recrystallization obtains white solid 19 (59.8g, 85% yield). ¹HNMR(300MHz，CDCl ₃)：δ＝7.43(d，J＝8.1Hz，4H)，7.25(d，J＝8.1Hz，4H)，7.16(d，J＝8.0Hz，4H)，7.08(d，J＝8.0Hz，4H)，4.57(s，2H)，4.33(s，2H)，2.40(s，6H)，2.32(s，6H)，1.09(s，6H). ¹³CNMR(75MHz，CDCl ₃)：δ＝143.39，140.10，137.34，136.87，129.00，128.74，128.23，127.82，109.50，81.22，78.13，27.49，21.41，21.35.HRMS(ESl)Calcd.forC ₃₅H ₄₂NO ₄ ⁺([M+NH ₄] ⁺)540.3108，found540.3109.

4th step: in 150mL round-bottomed flask, add chloroform 33mL, 4.32g (66.4mmol) sodium azide solid.Cooling, stirs, then in flask, adds 33mL trifluoroacetic acid, continues to stir 5-10 minute.Add 19 (9.0g, 16.6mol), chloroform (20mL) solution.Then slowly TFA/20%TfOH solution is added carefully.Dropwise, continue stirring 30 minutes, then return to room temperature.TLC detection reaction is complete.Reactant liquor pours trash ice aqueous mixtures into, continues to stir, and then uses the ammonia neutralization of 12-15% to neutral.Divide liquid yield chloroform layer with separatory funnel, aqueous phase utilizes dichloromethane extraction (100mLX2), merges organic phase, washing, anhydrous sodium sulfate drying, is spin-dried for removal solvent and obtains white solid (8.9g, yield 90%).[α] ³⁰ _D＝-39.5°(c＝0.52，CHCl ₃). ¹HNMR(300MHz，CDCl ₃)：δ＝7.28-7.10(m，16H)，4.93(s，2H)，2.38(s，6H)，2.33(s，6H)，1.15(s，6H). ¹³CNMR(75MHz，CDCl ₃)：δ＝139.29，137.58，129.75，128.95，128.58，128.40，110.68，80.78，73.26，27.77，21.39，21.34.IR(KBr)：3026，2988，2923，2106，1510，1380，1369，1242，1218，1165，1071，1021，924，878，811，785，752，574cm ^-1.HRMS(ESI)Calcd.forC ₃₅H ₃₆N ₆O ₂Na ⁺([M+Na] ⁺)595.2797，found595.2788.

Under an argon atmosphere, lithium aluminium hydride reduction (2.6g, 69.6mmol, 6.0equiv) and anhydrous tetrahydro furan (93mL) is added in there-necked flask; Oxolane (93mL) solution of product azide (6.9g, 11.6mmol, 1.0equiv) slowly drips to there-necked flask, and dropwise, reaction system slowly returns to room temperature; Continue to stir, TLC detection reaction is complete, adds sodium sulphate saturated aqueous solution and destroys too much lithium aluminium hydride reduction, then filter, and washing, is spin-dried for.Use acetic acid ethyl dissolution crude product, saturated aqueous common salt repeatedly washs, then anhydrous magnesium sulfate drying; Filter, be spin-dried for, after vacuum drying, obtain white solid (20).Be recrystallized in n-hexane and ethyl acetate mixed solvent, obtain clear crystal 5.9g, yield 98%yield. [α] ³¹ _d=-41.0 ° of (c=0.54, CHCl ₃). ¹hNMR (300MHz, CDCl ₃): δ=7.42 (d, J=8.1Hz, 4H), 7.15 (d, J=8.0Hz, 4H), 7.04 (q, J=8.5Hz, 8H), 4.24 (s, 2H), 2.40 (s, 6H), 2.28 (d, J=5.9Hz, 10H), 1.15 (s, 6H). ¹³cNMR (75MHz, CDCl ₃): δ=147.53,141.37,136.56,136.16,129.44,128.97,128.32,127.76,107.67,82.30,62.38,27.65,21.50,21.36.IR (KBr): 3363,3295,3249,3166,3090,3022,2981,2920,2877,1581,1510,1453,1376,1367,1236,1172,1066,1020,894,814,776,744,723,606,548cm ^-1.HRMS (ESI) Calcd.forC ₃₅h ₄₁n ₂o ₂ ⁺([M+H] ⁺) 521.3163, found521.3163.

5th step: add TADDamine20 (2.1g in there-necked flask, 4.0mmol) with triethylamine (1.4mL, 10mmol), toluene 10mL, then phosphorus pentachloride (0.42g is slowly dripped, toluene solution (10mL) 2.0mmol), dropwises, and is heated to 110 DEG C of reactions 2 hours.Reaction system returns to room temperature, crosses the triethylamine hydrochloride filtering generation, is spin-dried for and obtains crude product; Crude product is recrystallized in acetone and obtains catalyst precarsor, without the need to being further purified, directly carries out next step reaction.

6th step: be directly dissolved in tetrahydrofuran solution by the compound obtained in the 5th step, slowly add potassium hydroxide aqueous solution and be neutralized to neutrality, separatory, is spin-dried for the crude product that tetrahydrofuran solution obtains I-7, then obtains clear crystal by re-crystallizing in ethyl acetate; The overall yield of two steps is 94% (2.0g).[α] ³¹ _D＝-77.3°(c＝0.68，CHCl ₃). ¹HNMR(300MHz，CDCl ₃)：δ＝7.62-6.34(m，32H)，4.96(d，J＝46.1Hz，4H)，2.83(brs，3H)，2.38(s，12H)，2.29(s，12H)，0.81(d，J＝33.2Hz，12H). ¹³CNMR(100MHz，CDCl ₃)：δ＝144.91，140.99，135.79，129.78，128.49，127.82，127.53，109.83，82.39，77.36，65.75，27.12，21.23，21.00. ³¹PNMR(121MHz，CDCl ₃)：δ＝-6.46(s).IR(KBr)：3363，3023，2987，2921，2867，1509，1455，1406，1379，1244，1216，1164，1058，1019，907，888，827，808，786，755，716cm ^-1.HRMS(MALDI/DHB)：CalcdforC ₇₀H ₇₆N ₄O ₄P ⁺([M+H] ⁺)1067.5599，found1067.5598.

Embodiment 8: the synthesis of phosphazene catalyst I-8

3rd step: under an argon atmosphere, there-necked flask installs return channel, the dropping funel of band equilibrated valve, and a thermometer; Then fresh magnesium rod (14.1g, 579mmol, 1.02equiv.) and a fritter iodine is added as initator.Then in dropping funel, add 4-bromofluorobenzene (96g, tetrahydrofuran solution (386mL) 551mmol). slowly drip, until reaction starts. constantly drop to complete, add hot reflux and continue reaction one hour, be then cooled to room temperature.

In above-mentioned grignard reagent, add dimethyl dimethyl tartrate 2 (24.1g, 124mmol), slowly add, ensure that temperature is no more than 20 degree, after being added dropwise to complete, reaction system adds hot reflux 1.5 hours, is then cooled to room temperature.Slowly add saturated ammonium chloride solution quencher reaction, be extracted with ethyl acetate three times (40mLX3), then anhydrous magnesium sulfate drying; Filter, be spin-dried for, after vacuum drying, obtain micro-yellow foamy solid; In carrene and methyl alcohol, recrystallization obtains micro-yellow solid 21 (53.3g, 80% yield). ¹HNMR(300MHz，CDCl ₃)：δ＝7.48(dd，J＝8.6，5.6Hz，4H)，7.26(dd，J＝8.8，5.4Hz，4H)，7.03(t，J＝8.7Hz，4H)，6.94(t，J＝8.7Hz，4H)，4.37(s，2H)，3.23(s，2H)，1.07(s，6H). ¹³CNMR(75MHz，CDCl ₃)：δ＝163.84(d，J＝12.2Hz)，160.57(d，J＝13.0Hz)，141.49(d，J＝3.2Hz)，138.07(d，J＝3.1Hz)，130.36(d，J＝7.9Hz)，129.56(d，J＝8.1Hz)，115.08(d，J＝21.3Hz)，114.32(d，J＝21.2Hz)，109.61，80.89，77.52，27.17. ¹⁹FNMR(282MHz，CDCl ₃)：δ＝-113.05--113.18(m)，-113.90--114.04(m).HRMS(ESI)Calcd.forC ₃₁H ₂₅F ₄O ₄ ^-([M-H] ^-)537.1689，found537.1698.

4th step: in 150mL round-bottomed flask, add chloroform 33mL, 4.32g (66.4mmol) sodium azide solid.Cooling, stirs, then in flask, adds 33mL trifluoroacetic acid, continues to stir 5-10 minute.Add 21 (8.9g, 16.6mol), chloroform (20mL) solution.Then slowly TFA/20%TfOH solution is added carefully.Dropwise, continue stirring 30 minutes, then return to room temperature.TLC detection reaction is complete.Reactant liquor pours trash ice aqueous mixtures into, continues to stir, and then uses the ammonia neutralization of 12-15% to neutral.Divide liquid yield chloroform layer with separatory funnel, aqueous phase utilizes dichloromethane extraction (100mLX2), merges organic phase, washing, anhydrous sodium sulfate drying, is spin-dried for removal solvent and obtains white solid (6.9g, yield 75%).[α] ²⁹ _D＝-23.4°(c＝0.52，CHCl ₃). ¹HNMR(300MHz，CDCl ₃)：δ＝7.40-7.23(m，8H)，7.07(dd，J＝14.9，8.3Hz，8H)，4.83(s，2H)，1.19(s，6H). ¹³CNMR(75MHz，CDCl ₃)：δ＝163.84，163.63，160.55，160.34，137.38，137.33，135.57，135.53，131.18，131.08，130.00，129.89，115.20，114.92，114.80，114.52，110.52，80.32，72.02，27.28. ¹⁹FNMR(282MHz，CDCl ₃)：δ＝-112.35--112.48(m)，-112.52--112.65(m).IR(KBr)：3075，2992，2912，2883，2108，1603，1507，1371，1227，1164，1070，1015，978，881，836，757，729，684，588，569cm ^-1.HRMS(ESI)Calcd.forC ₃₁H ₂₅F ₄N ₄O ₂ ⁺([M-N ₂+H] ⁺)561.1908，found561.1757.

Under an argon atmosphere, lithium aluminium hydride reduction (2.6g, 69.6mmol, 6.0equiv) and anhydrous tetrahydro furan (93mL) is added in there-necked flask; THF (93mL) solution of product azide (6.5g, 11.6mmol, 1.0equiv) slowly drips to there-necked flask, and dropwise, reaction system slowly returns to room temperature; Continue to stir, TLC detection reaction is complete, adds sodium sulphate saturated aqueous solution and destroys too much lithium aluminium hydride reduction, then filter, and washing, is spin-dried for.Use acetic acid ethyl dissolution crude product, saturated aqueous common salt repeatedly washs, then anhydrous magnesium sulfate drying; Filter, be spin-dried for, after vacuum drying, obtain white solid (22).Be recrystallized in n-hexane and ethyl acetate mixed solvent, obtain clear crystal 5.9g, yield 98%yield.[α] ³¹ _D＝-41.0°(c＝0.54，CHCl ₃). ¹HNMR(300MHz，CDCl ₃)：δ＝7.42(d，J＝8.1Hz，4H)，7.15(d，J＝8.0Hz，4H)，7.04(q，J＝8.5Hz，8H)，4.24(s，2H)，2.40(s，6H)，2.28(d，J＝5.9Hz，10H)，1.15(s，6H). ¹³CNMR(75MHz，CDCl ₃)：δ＝147.53，141.37，136.56，136.16，129.44，128.97，128.32，127.76，107.67，82.30，62.38，27.65，21.50，21.36.IR(KBr)：3363，3295，3249，3166，3090，3022，2981，2920，2877，1581，1510，1453，1376，1367，1236，1172，1066，1020，894，814，776，744，723，606，548cm ^-1.HRMS(ESI)Calcd.forC ₃₅H ₄₁N ₂O ₂ ⁺([M+H] ⁺)521.3163，found521.3163.

5th step: add TADDamine22 (2.1g in there-necked flask, 4.0mmol) with triethylamine (1.4mL, 10mmol), toluene 10mL, then phosphorus pentachloride (0.42g is slowly dripped, toluene solution (10mL) 2.0mmol), dropwises, and is heated to 110 DEG C of reactions 2 hours.Reaction system returns to room temperature, crosses the triethylamine hydrochloride filtering generation, is spin-dried for and obtains crude product; Crude product is recrystallized in acetone and obtains catalyst precarsor, without the need to being further purified, directly carries out next step reaction.

6th step: be directly dissolved in tetrahydrofuran solution by the compound obtained in the 5th step, slowly add potassium hydroxide aqueous solution and be neutralized to neutrality, separatory, is spin-dried for the crude product that tetrahydrofuran solvent obtains I-8, then obtains clear crystal by re-crystallizing in ethyl acetate; The overall yield of two steps is 90% (1.9g).[α] ³¹ _D＝-72.1°(c＝0.55，CHCl ₃). ¹HNMR(300MHz，CDCl ₃)：δ＝7.48(s，8H)，7.37-7.07(m，8H)，7.05-6.83(m，16H)，4.88(s，4H)，2.75(s，3H)，0.84(s，12H). ¹³CNMR(100MHz，CDCl ₃)：δ＝163.00，162.81，160.54，160.36，143.04，139.13，131.37，129.04，128.96，115.00，114.85，114.31，114.14，110.59，83.11，80.98，77.30，65.32，26.89. ³¹PNMR(121MHz，CDCl ₃)：δ＝-7.68(s). ¹⁹FNMR(282MHz，CDCl ₃)：δ＝-114.39(s)，-115.53(s).IR(KBr)：3368，3063，2988，2935，1604，1507，1406，1381，1238，1162，1057，1014，908，889，826，763，716，593，575，559cm ^-1.HRMS(MALDI/DHB)：CalcdforC ₆₂H ₆₂N ₄O ₄F ₈P ⁺([M+H] ⁺)1099.3593，found1099.3600.

Embodiment 9: the synthesis of phosphazene catalyst I-9

3rd step: under an argon atmosphere, there-necked flask installs return channel, the dropping funel of band equilibrated valve, and a thermometer; Then fresh magnesium rod (14.1g, 579mmol, 1.02equiv.) and a fritter iodine is added as initator.Then in dropping funel, add 2-bromopyridine (87g, tetrahydrofuran solution (386mL) 551mmol). slowly drip, until reaction starts. constantly drop to complete, add hot reflux and continue reaction one hour, be then cooled to room temperature.

In above-mentioned grignard reagent, add dimethyl dimethyl tartrate 2 (24.1g, 124mmol), slowly add, ensure that temperature is no more than 20 degree, after being added dropwise to complete, reaction system adds hot reflux 1.5 hours, is then cooled to room temperature.Slowly add saturated ammonium chloride solution quencher reaction, be extracted with ethyl acetate three times (40mLX3), then anhydrous magnesium sulfate drying; Filter, be spin-dried for, after vacuum drying, obtain micro-yellow foamy solid; In carrene and methyl alcohol, recrystallization obtains white solid 23 (11g, 20% yield). ¹HNMR(300MHz，CDCl ₃)：δ＝8.5(m，4H)，7.9(m，4H)，7.7(m，4H)，7.4(s，4H)，4.62(s，2H)，1.4(s，6H).HRMS(ESI)Calcd.forC ₂₇H ₂₆N ₄O ₄ ⁺([M+NH ₄] ⁺)470.5197，found470.5199.

4th step: in 150mL round-bottomed flask, add chloroform 33mL, 4.32g (66.4mmol) sodium azide solid.Cooling, stirs, then in flask, adds 33mL trifluoroacetic acid, continues to stir 5-10 minute.Add chloroform (20mL) solution of 23 (7.8g, 16.6mol).Then slowly TFA/20%TfOH solution is added carefully.Dropwise, continue stirring 30 minutes, then return to room temperature.TLC detection reaction is complete.Reactant liquor pours trash ice aqueous mixtures into, continues to stir, and then uses the ammonia neutralization of 12-15% to neutral.Divide liquid yield chloroform layer with separatory funnel, aqueous phase utilizes dichloromethane extraction (100mLX2), merges organic phase, washing, anhydrous sodium sulfate drying, is spin-dried for removal solvent and obtains white solid (3.4g, yield 40%). and [α] ³⁰ _d=+35.0 ° of (c=0.52, CHCl ₃). ¹hNMR (300MHz, CDCl ₃): δ=8.5 (m, 4H), 7.6 (m, 4H), 7.3 (m, 8H), 4.5 (s, 2H), 1.21 (s, 6H). ¹³cNMR (75MHz, CDCl ₃): δ=166.12,149.20,124.48,123.66,122.53,90.46,85.23,70.21,23.90.HRMS (ESI) Calcd.forC ₂₇h ₂₄n ₁₀o ₂na ⁺([M+Na] ⁺) 543.5350, found543.5350.

Under an argon atmosphere, lithium aluminium hydride reduction (2.6g, 69.6mmol, 6.0equiv) and anhydrous tetrahydro furan (93mL) is added in there-necked flask; THF (93mL) solution of azide (6.1g, 11.6mmol, 1.0equiv) slowly drips to there-necked flask, and dropwise, reaction system slowly returns to room temperature; Continue to stir, TLC detection reaction is complete, adds sodium sulphate saturated aqueous solution and destroys too much lithium aluminium hydride reduction, then filter, and washing, is spin-dried for.Use acetic acid ethyl dissolution crude product, saturated aqueous common salt repeatedly washs, then anhydrous magnesium sulfate drying; Filter, be spin-dried for, after vacuum drying, obtain white solid (24).Be recrystallized in n-hexane and ethyl acetate mixed solvent, obtain clear crystal 4.8g, yield 90%yield. [α] ³¹ _d=-83.0 ° of (c=0.53, CHCl ₃). ¹hNMR (300MHz, CDCl ₃): δ=8.54 (d, J=6.5Hz, 4H), 7.75 (m, 4H), 7.50 (d, J=7.5Hz, 4H), 7.35 (m, 4H), 5.12 (brs, 4H), 4.88 (s, 2H), 1.25 (s, 6H). ¹³cNMR (75MHz, CDCl ₃): δ=163.97,148.21,137.48,125.56,123.59,121.66,92.29,61.78,21.90.HRMS (ESI) Calcd.forC ₃₉h ₄₉n ₂o ₂ ⁺([M+H] ⁺) 469.5582, found469.5585.

5th step: add 24 (1.9g in there-necked flask, 4.0mmol) with triethylamine (1.4mL, 10mmol), toluene 10mL, then phosphorus pentachloride (0.42g is slowly dripped, toluene solution (10mL) 2.0mmol), dropwises, and is heated to 110 DEG C of reactions 2 hours.Reaction system returns to room temperature, crosses the triethylamine hydrochloride filtering generation, is spin-dried for and obtains crude product; Crude product is recrystallized in acetone and obtains catalyst precarsor, without the need to being further purified, directly carries out next step reaction.

6th step: the compound obtained in the 5th step is directly dissolved in tetrahydrofuran solution, slowly adds potassium hydroxide aqueous solution and be neutralized to neutrality, separatory, be spin-dried for tetrahydrofuran solution and obtain crude product, then obtain clear crystal with ethyl alcohol recrystallization; The overall yield of two steps is 91% (1.7g). [α] ³² _d=-158.1 ° of (c=0.9, CHCl ₃). ¹hNMR (300MHz, CDCl ₃): δ=8.62-7.08 (m, 32H), 4.93 (s, 4H), 4.16 (d, J=101.6Hz, 4H), 2.0 (s, 3H), 1.62-0.21 (m, 12H). ¹³cNMR (100MHz, CDCl ₃): δ=164.07,148.70,138.55,136.93,136.55,128.16,126.85,125.19,111.15,107.66,94.11,90.44,54.29,21.56. ³¹pNMR (121MHz, CDCl ₃): δ=-13.17 (s) .HRMS (MALDI/DHB): CalcdforC ₇₈h ₉₂n ₄o ₄p ⁺([M+H] ⁺) 964.0424, found964.0420.

Embodiment 10: the synthesis of phosphazene catalyst II-1

The first step: the synthetic method as I-1: under an argon atmosphere, adds L-trans cvclohexvl diacid 25 (172g, 1mol), absolute methanol (500mL) in reaction bulb; Be cooled to zero degree, slowly drip thionyl chloride (145mL, 2mol), dropwise back flow reaction 1 hour.After reaction system cool to room temperature, take hydrogen chloride gas and unnecessary methyl alcohol away.With water (100mL) quencher, be extracted with ethyl acetate three times (40mLX3), then anhydrous magnesium sulfate drying; Filter, be spin-dried for, after vacuum drying, obtain oily liquids 26 (199g, 126mmol, 99%): ¹hNMR (300MHz, CDCl ₃): δ=3.68 (s, 6H), 2.90 (m, 2H), 1.43-1.99 (m, 8H).

Second step: under an argon atmosphere, there-necked flask installs return channel, the dropping funel of band equilibrated valve, and a thermometer; Then fresh magnesium rod (14.1g is added, 579mmol, 1.02equiv.) He one fritter iodine is as initator. then in dropping funel, add bromobenzene (86.5g, tetrahydrofuran solution (386mL) 551mmol). then slowly drip, until reaction starts. dropwise, add hot reflux and continue reaction one hour, be then cooled to room temperature.

In above-mentioned grignard reagent, add cyclohexane diacid dimethyl ester 26 (25.0g, 125mmol), slowly add, ensure that temperature is no more than 20 degree, after being added dropwise to complete, reaction system adds hot reflux 1.5 hours, is then cooled to room temperature.Slowly add saturated aqueous ammonium chloride quencher reaction, be extracted with ethyl acetate three times (400mLX3), then anhydrous magnesium sulfate drying; Filter, be spin-dried for, after vacuum drying, obtain crude product; In carrene and methyl alcohol, recrystallization obtains white solid 27 (39.2g, 70%yield). ¹HNMR(300MHz，CDCl ₃)：δ＝7.48-7.41(m，4H)，7.38-7.22(m，16H)，2.27-2.41(m，2H)，1.43-1.52(m，8H).HRMS(ESI)Calcd.forC ₃₂H ₃₂O ₂ ⁺([M] ⁺)448.2402，found448.2401.

3rd step: in 150mL round-bottomed flask, add chloroform 33mL, 4.32g (66.4mmol) sodium azide solid.Stir, then in flask, add 33mL trifluoroacetic acid, continue to stir 5-10 minute.Add chloroform (20mL) solution of 7.4g (16.6mmol) 27.Then slowly TFA/20%TfOH solution is added carefully.Dropwise, continue stirring 30 minutes, then return to room temperature.TLC detection reaction is complete.Reactant liquor pours trash ice aqueous mixtures into, continues to stir, and is then neutralized to neutrality with the liquefied ammonia of 12-15%.Divide liquid yield chloroform layer with separatory funnel, aqueous phase utilizes dichloromethane extraction (100mLX2), merges organic phase, washing, anhydrous sodium sulfate drying, is spin-dried for removal solvent and obtains crude product.

Lithium aluminium hydride reduction (3.7g, 99.6mmol, 6.0equiv) and absolute ether (100mL) is added in there-necked flask; THF (100mL) solution of the azide in previous step slowly drips to there-necked flask, and dropwise, reaction system slowly returns to room temperature; Continue to stir, TLC detection reaction is complete.Add sodium sulphate saturated aqueous solution and destroy too much lithium aluminium hydride reduction, then filter, washing, is spin-dried for.Use acetic acid ethyl dissolution crude product, saturated aqueous common salt repeatedly washs, then anhydrous magnesium sulfate drying; Filter, be spin-dried for, after vacuum drying, obtain white solid (28).In n-hexane and ethyl acetate mixtures, recrystallization obtains clear crystal, yield 90%. ¹HNMR(300MHz，CDCl ₃)：δ＝7.62-7.51(m，4H)，7.39-7.28(m，6H)，7.27-7.13(m，10H)，5.42(s，4H)，2.42-2.43(m，2H)，1.27-1.53(m，8H). ¹³CNMR(75MHz，CDCl ₃)：δ＝150.40，144.10，129.57，128.22，127.89，127.48，127.24，127.18，126.65，81.66，63.01，43.85，26.5，23.6.HRMS(ESI)Calcd.forC ₃₂H ₃₄N ₂ ⁺([M+H] ⁺)447.2800，found447.2802.

4th step: add 28 (1.80g in there-necked flask, 4.0mmol) with triethylamine (1.4mL, 10mmol), toluene 10mL, then phosphorus pentachloride (0.42g is slowly dripped, toluene solution (10mL) 2.0mmol), dropwises, and is heated to 110 DEG C of reactions 2 hours.Reaction system returns to room temperature, crosses the triethylamine hydrochloride filtering generation, is spin-dried for and obtains crude product 29.

5th step: precursor 29 is directly dissolved in tetrahydrofuran solution, slowly add potassium hydroxide aqueous solution and be neutralized to neutrality, separatory, be spin-dried for tetrahydrofuran solution and obtain catalyst I I-1 crude product, then clear crystal 1.5g is obtained by re-crystallizing in ethyl acetate, two step overall yield 80%.[α] ³¹ _D＝-102.1°(c＝0.59，CHCl ₃). ¹HNMR(300MHz，CDCl ₃)：δ＝7.70-6.49(m，40H)，2.51(d，J＝50.6Hz，2H)，2.11(d，J＝61.6Hz，2H)，2.80(s，3H)，1.58-1.11(m，16H). ¹³CNMR(100MHz，CDCl ₃)：δ＝142.20，138.23，124.58，122.72，122.60，122.19，121.80，121.35，59.27，53.2，41.6，26.60，23.9. ³¹PNMR(121MHz，CDCl ₃)：δ＝-6.94(s).HRMS(MALDI/DHB)：CalcdforC ₆₄H ₆₃N ₄P ⁺([M+H] ⁺)920.1935，found920.1936.

Embodiment 11: asymmetric catalysis application example

Oxoindole derivative is extensively present in nature, and major part sees in relevant natural products and pharmaceutically active molecule with optically active form.Therefore prepare optically-active pure zirconia indoles and there is suitable status in new drug development.Therefore we utilize 3-to replace Oxoindole as reaction substrate, and utilize the New Phosphorus nitrile catalyst catalytic halogenation of above-mentioned preparation to react, almost quantitative yield and very outstanding enantioselectivity have prepared 3-chloro-3-Oxoindole compound.In catalytic process, catalyst can realize effective recovery, and is amplified to tens grams, does not occur the decline of the reduction of significant efficiency and enantioselectivity.

Experimental procedure: single port reaction flask adds Oxoindole raw material (0.1mmol, 1.0equiv), phosphazene catalyst (7mg, 0.005mmol, 5mol%) is dissolved in 1mL ether; Magnetic agitation, chlorination reagent NCS (0.12mmol, 1.2equiv) add in batches, about 10 minutes of joining day. then stir five minutes, reactant directly carries out purifies and separates by silica gel chromatographic column and obtains corresponding chlorizate 16, and yield and polarimetry purity are shown in above-mentioned chemical formula table data.The ee value of product 30 is carried out analysis by chromatograph and chiral chromatographic column and is obtained.

(30a): 99% yield, 99%ee. enantiomeric purity analysis condition: (ChiralcelOJ-H, 1.0mL/min, 254nm, 9:1hexanes/iPrOH): t _r(major)=7.05min, t _r(minor)=9.34min. [α] ³¹ _d=+128.5 ° of (c=1.10, CHCl ₃), Lit:[α] ²⁰ _d=-81.9 ° of (c=0.18, CHCl ₃, (R)-isomer) ². ¹hNMR (300MHz, CDCl ₃): δ=8.00 (d, J=8.1Hz, 1H), 7.57-7.23 (m, 8H), 1.63 (s, 9H). ¹³cNMR (75MHz, CDCl ₃): δ=171.20,149.19,139.32,136.54,131.03,129.43,129.09,128.82,128.11,126.36,125.68,115.88,85.41,66.80,28.26.MS (EI) (relativeintensity): m/z343 (M ⁺), 245 (12.18), 244 (7.79), 243 (33.48), 242 (8.83), 210 (5.21), 209 (38.99), 208 (100), 180 (21.02), 57 (23.88).

(30b): 98% yield, 98%ee. enantiomeric purity analysis condition: (ChiralcelOJ-H, 1.0mL/min, 254nm, 9:1hexanes/iPrOH): t _r(major)=6.46min, t _r(minor)=5.13min. [α] ³⁰ _d=+106.6 ° of (c=1.18, CHCl ₃). ¹hNMR (300MHz, CDCl ₃): δ=8.01 (dd, J=8.6,4.3Hz, 1H), 7.57-7.45 (m, 2H), 7.44-7.32 (m, 3H), 7.22-7.08 (m, 2H), 1.62 (s, 9H). ¹³cNMR (75MHz, CDCl ₃): δ=170.80,162.01,158.76,149.13,135.98,135.30,135.27,130.84,130.73,129.64,128.95,127.90,118.01,117.70,117.55,117.45,113.70,113.37,85.62,66.39,28.22. ¹⁹fNMR (282MHz, CDCl ₃): δ=-116.12 (td, J=8.1,4.8Hz) .MS (EI) (relativeintensity): m/z361 (M ⁺), 263 (16.1), 262 (8.47), 261 (45.47), 260 (7.96), 227 (32.38), 226 (100), 225 (7.25), 224 (6.11), 198 (20.08), 57 (28.98).

(30c): 95% yield, 94%ee. enantiomeric purity analysis condition: (ChiralcelAS-H, 1.0mL/min, 254nm, 100:1hexanes/iPrOH): t _r(major)=12.25min, t _r(minor)=13.47min. [α] ³¹ _d=+95.7 ° of (c=1.06, CHCl ₃). ¹hNMR (300MHz, CDCl ₃): δ=7.57-7.45 (m, 2H), 7.43-7.31 (m, 3H), 7.30-7.14 (m, 3H), 1.60 (s, 9H). ¹³cNMR (75MHz, CDCl ₃): δ=170.78,150.42,147.26,147.07,135.94,132.29,132.28,129.64,128.94,127.87,126.77,126.68,126.35,126.21,122.21,122.16,119.24,118.97,86.11,66.68,66.65,27.91. ¹⁹fNMR (282MHz, CDCl ₃): δ=-118.73 (dd, J=10.2,3.3Hz) .MS (EI) (relativeintensity): m/z361 (M ⁺), 263 (10.88), 262 (8.55), 261 (34.61), 260 (12.49), 227 (29.07), 226 (100), 225 (6.24), 224 (7.83), 198 (15.4), 57 (26.41).

(30d): 96% yield, 93%ee. enantiomeric purity analysis condition: (ChiralcelAS-H, 1.0mL/min, 254nm, 100:1hexanes/iPrOH): t _r(major)=7.46min, t _r(minor)=8.10min. [α] ³⁰ _d=+123.5 ° of (c=1.06, CHCl ₃). ¹hNMR (300MHz, CDCl ₃): δ=7.87 (d, J=8.2Hz, 1H), 7.59-7.46 (m, 2H), 7.42-7.30 (m, 3H), 7.29-7.19 (m, 2H), 2.38 (s, 3H), 1.63 (s, 9H). ¹³cNMR (75MHz, CDCl ₃): δ=171.36,149.24,136.94,136.69,135.52,131.64,129.36,129.05,128.79,128.10,126.65,115.69,85.22,67.08,28.27,21.35.MS (EI) (relativeintensity): m/z357 (M ⁺), 259 (13.15), 258 (9.28), 257 (40.01), 256 (8.41), 223 (22.53), 222 (100), 221 (6.16), 192 (8.58), 57 (14.01).

(30e): 95% yield, 93%ee. enantiomeric purity analysis condition: (ChiralcelOJ-H, 1.0mL/min, 254nm, 9:1hexanes/iPrOH): t _r(major)=12.94min, t _r(minor)=9.31min. [α] ³⁰ _d=+106.1 ° of (c=1.41, CHCl ₃). ¹hNMR (300MHz, CDCl ₃): δ=7.91 (d, J=8.8Hz, 1H), 7.59-7.45 (m, 2H), 7.43-7.27 (m, 3H), 7.04-6.87 (m, 2H), 3.79 (s, 3H), 1.61 (s, 9H). ¹³cNMR (75MHz, CDCl ₃): δ=171.26,157.64,149.25,136.53,132.57,130.16,129.43,128.83,128.07,117.01,116.58,111.48,85.18,67.12,55.97,28.26.MS (EI) (relativeintensity): m/z373 (M ⁺), 275 (19.85), 274 (12.02), 273 (62.4), 272 (7.06), 239 (28.64), 238 (100), 237 (5.41), 210 (5.81), 57 (19.75).

(30f): 99% yield, 96%ee. enantiomeric purity analysis condition (ChiralcelOJ-H, 0.3mL/min, 254nm, 9:1hexanes/iPrOH): t _r(major)=19.31min, t _r(minor)=21.21min. [α] ³⁰ _d=+113.4 ° of (c=0.96, CHCl ₃). ¹hNMR (300MHz, CDCl ₃): δ=7.99 (d, J=8.2Hz, 1H), 7.58-7.37 (m, 4H), 7.35-7.23 (m, 1H), 7.04 (t, J=8.6Hz, 2H), 1.62 (s, 9H). ¹³cNMR (75MHz, CDCl ₃): δ=171.03,165.02,161.71,149.09,139.30,132.42,132.38,131.20,130.35,130.24,128.68,126.30,125.74,115.98,115.91,115.62,85.53,66.08,28.23. ¹⁹fNMR (282MHz, CDCl ₃): δ=-112.46--112.66 (m) .MS (EI) (relativeintensity): m/z361 (M ⁺), 263 (10.09), 262 (8.10), 261 (29.03), 260 (9.74), 227 (24.2), 226 (100), 225 (5.95), 224 (5.21), 198 (10.37), 57 (22.47).

(30g): 98% yield, 99%ee. enantiomeric purity analysis condition (ChiralcelAD-H, 0.6mL/min, 214nm, 100:1hexanes/iPrOH): t _r(major)=9.66min, t _r(minor)=10.75min. [α] ³⁰ _d=+116.6 ° of (c=0.99, CHCl ₃). ¹hNMR (300MHz, CDCl ₃): δ=8.00 (dd, J=8.8,4.4Hz, 1H), 7.54-7.41 (m, 2H), 7.22-7.10 (m, 2H), 7.06 (t, J=8.6Hz, 2H), 1.61 (s, 9H). ¹³cNMR (75MHz, CDCl ₃): δ=170.63,165.11,162.02,161.79,158.76,149.04,135.28,135.24,131.86,131.81,130.40,130.29,130.16,130.04,118.20,117.90,117.68,117.58,116.08,115.79,113.63,113.30,85.73,65.68,28.19. ¹⁹fNMR (282MHz, CDCl ₃): δ=-112.01--112.15 (m) ,-115.84--115.98 (m) .MS (EI) (relativeintensity): m/z379 (M ⁺), 281 (13.08), 280 (9.30), 279 (38.38), 278 (10.77), 245 (27.87), 244 (100), 243 (5.95), 242 (5.03), 216 (14.82), 57 (32.75).,

(30h): 97% yield, 99%ee. enantiomeric purity analysis condition (ChiralcelOJ-H, 1.0mL/min, 254nm, 9:1hexanes/iPrOH): t _r(major)=8.23min, t _r(minor)=19.73min. [α] ³⁰ _d=+111.8 ° of (c=0.94, CHCl ₃). ¹hNMR (300MHz, CDCl ₃): δ=7.49 (dd, J=8.9,5.1Hz, 2H), 7.32-7.16 (m, 3H), 7.05 (t, J=8.6Hz, 2H), 1.60 (s, 9H). ¹³cNMR (75MHz, CDCl ₃): δ=170.60,165.11,161.79,150.45,147.16,147.10,131.88,131.86,131.82,131.78,130.16,130.05,126.84,126.75,126.35,126.21,122.16,122.11,119.43,119.16,116.07,115.78,86.24,65.94,65.91,27.88. ¹⁹fNMR (282MHz, CDCl ₃): δ=-112.03--112.17 (m) ,-118.52 (dd, J=10.9,3.7Hz) .MS (EI) (relativeintensity): m/z379 (M ⁺), 281 (8.67), 280 (7.64), 279 (24.7), 278 (13.31), 245 (26.70), 244 (100), 243 (5.85), 242 (5.61), 216 (11.98), 57 (27.06).

(30i): 95% yield, 95%ee. enantiomeric purity analysis condition (ChiralcelAS-H, 0.6mL/min, 214nm, 100:1hexanes/iPrOH): t _r(major)=7.80min, t _r(minor)=8.49min. [α] ³⁰ _d=+122.6 ° of (c=1.00, CHCl ₃). ¹hNMR (300MHz, CDCl ₃): δ=7.86 (d, J=8.3Hz, 1H), 7.50 (dd, J=8.8,5.2Hz, 2H), 7.30-7.17 (m, 2H), 7.04 (t, J=8.6Hz, 2H), 2.38 (s, 3H), 1.62 (s, 9H). ¹³cNMR (75MHz, CDCl ₃): δ=171.20,164.98,161.67,149.14,136.91,135.63,132.55,132.51,131.82,130.34,130.23,128.62,126.58,115.88,115.78,115.59,85.34,66.35,28.23,21.33. ¹⁹fNMR (282MHz, CDCl ₃): δ=-112.62--112.76 (m) .MS (EI) (relativeintensity): m/z375 (M ⁺), 277 (12.5), 276 (9.02), 275 (39.26), 274 (9.02), 241 (24.09), 240 (100), 239 (7.33), 238 (5.63), 210 (8.94), 57 (20.50).

(30j): 98% yield, 99%ee. enantiomeric purity analysis condition (ChiralcelAD-H, 0.6mL/min, 214nm, 100:1hexanes/iPrOH): t _r(major)=10.14min, t _r(minor)=11.58min. [α] ³⁰ _d=+89.1 ° of (c=1.03, CHCl ₃). ¹hNMR (300MHz, CDCl ₃): δ=8.00 (dd, J=9.2,4.3Hz, 1H), 7.38 (d, J=8.2Hz, 2H), 7.25-7.09 (m, 4H), 2.35 (s, 3H), 1.62 (s, 9H). ¹³cNMR (75MHz, CDCl ₃): δ=170.89,161.99,158.74,149.19,139.79,135.26,135.23,133.02,130.94,130.83,129.64,127.83,117.91,117.61,117.49,117.39,113.68,113.35,85.53,66.37,66.35,28.22,21.36. ¹⁹fNMR (282MHz, CDCl ₃): δ=-116.26 (td, J=8.0,4.8Hz) .MS (EI) (relativeintensity): m/z375 (M ⁺), 277 (10.68), 276 (8.24), 275 (26.79), 274 (8.46), 241 (27.87), 240 (100), 239 (5.80), 211 (10.1), 57 (22.67).

(30k): 93% yield, 90%ee. enantiomeric purity analysis condition (ChiralcelOJ-H, 1.0mL/min, 254nm, 9:1hexanes/iPrOH): t _r(major)=6.71min, t _r(minor)=12.55min. [α] ³⁰ _d=+94.8 ° of (c=1.30, CHCl ₃). ¹hNMR (300MHz, CDCl ₃): δ=8.00 (d, J=8.1Hz, 1H), 7.51-7.35 (m, 4H), 7.29 (t, J=7.6Hz, 1H), 7.18 (d, J=7.8Hz, 2H), 2.35 (s, 3H), 1.63 (s, 9H). ¹³cNMR (75MHz, CDCl ₃): δ=171.27,149.24,139.53,139.30,133.59,130.95,129.51,129.17,128.06,126.35,125.62,115.84,85.32,66.75,28.25,21.38.MS (EI) (relativeintensity): m/z357 (M ⁺), 259 (8.41), 258 (6.81), 257 (25.94), 256 (10.78), 223 (33.26), 222 (100), 221 (7.42), 193 (9.29), 57 (16.19).

(30I): 93% yield, 99%ee. enantiomeric purity analysis condition (ChiralcelOJ-H, 1.0mL/min, 254nm, 9:1hexanes/iPrOH): t _r(major)=7.98min, t _r(minor)=16.37min. [α] ³⁰ _d=+59.8 ° of (c=1.06, CHCl ₃). ¹hNMR (300MHz, CDCl ₃): δ=8.07 (d, J=8.3Hz, 1H), 7.93-7.74 (m, 5H), 7.58-7.44 (m, 4H), 7.34 (t, J=7.5Hz, 1H), 1.65 (s, 9H). ¹³cNMR (75MHz, CDCl ₃): δ=171.17,149.24,139.41,133.80,133.50,132.74,131.15,129.05,128.76,127.83,127.60,127.47,126.93,126.49,125.78,125.41,115.98,85.46,67.09,28.27.MS (E1) (relativeintensity): m/z393 (M ⁺), 295 (7.68), 294 (7.25), 293 (26.69), 292 (8.72), 260 (11.16), 259 (61.56), 258 (100), 257 (10.90), 256 (7.31), 230 (28.34), 57 (23.58).

(30m): 94% yield, 90%ee. enantiomeric purity analysis condition (ChiralcelAD-H, 0.5mL/min, 214nm, 100:1hexanes/iPrOH): t _r(major)=13.92min, t _r(minor)=15.61min. [α] ³¹ _d=+8.6 ° of (c=0.97, CHCl ₃). ¹hNMR (300MHz, CDCl ₃): δ=7.65 (d, J=8.1Hz, 1H), 7.31 (dd, J=17.8,7.9Hz, 2H), 7.24-7.04 (m, 4H), 6.94 (d, J=6.6Hz, 2H), 3.58 (q, J=13.3Hz, 2H), 1.58 (s, 9H). ¹³cNMR (75MHz, CDCl ₃): δ=172.09,148.65,139.05,133.17130.74,130.66,128.33,127.75,127.62,125.13,125.03,115.43,85.06,65.69,46.28,28.23.MS (EI) (relativeintensity): m/z357 (M ⁺), 260 (5.42), 259 (31.45), 258 (20.14), 257 (100), 256 (9.6), 223 (6.99), 222 (16.50), 221 (12.02), 220 (18.85), 193 (15.66), 91 (87.7), 57 (40.96).

(30n): 97% yield, 90%ee. enantiomeric purity analysis condition (ChiralcelOJ-H, 0.3mL/min, 254nm, 9:1hexanes/iPrOH): t _r(major)=16.47min, t _r(minor)=18.49min. [α] ³⁰ _d=+71.1 ° of (c=0.95, CHCl ₃). ¹hNMR (300MHz, CDCl ₃): δ=7.86 (d, J=8.2Hz, 1H), 7.44 (d, J=7.5Hz, 1H), 7.36 (t, J=7.9Hz, 1H), 7.27-7.15 (m, 1H), 1.93 (s, 3H), 1.63 (s, 9H). ¹³cNMR (75MHz, CDCl ₃): δ=172.52,149.09,138.37,130.73,129.95,125.48,124.04,115.73,85.30,62.14,28.26,26.69.MS (EI) (relativeintensity): m/z281 (M ⁺), 183 (24.60), 182 (12.42), 181 (73.68), 180 (18.53), 147 (12.04), 146 (100), 145 (10.96), 128 (15.62), 117 (17.02), 57 (43.31).

The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after having read above-mentioned instruction content of the present invention.

Claims

1. based on a chiral phosphorus nitrile catalyst for the spirocyclic ring scaffold of chiral diamine, it is characterized in that containing multiple aromatic yl group or alkyl group, two heptatomic rings form spiro phosphine center, have following structural formula I or II:

In structural formula I or II:

R, R ' be selected from hydrogen, C ₁~ C ₂₀alkyl, C ₁~ C ₁₆perfluoroalkyl, C ₁~ C ₁₆perfluoroalkyl, C ₁~ C ₈containing fluoroalkyl replace aryl, C ₁~ C ₂₀the alkyl aryl, the aryl of halogen substiuted, the benzyl that the replace aryl, the C that replace ₁~ C ₄alkoxyl replace aryl, C ₆~ C ₁₂the aryl that replaces of aryl or containing the five-membered ring of O, N or S or the heteroaryl of hexatomic ring;

Described aryl is phenyl or naphthyl;

X=NH; N=0,1 or 2.

2. catalyst as claimed in claim 1, is characterized in that, R, R ' prioritizing selection C ₁~ C ₄alkyl replace aryl, F, Cl or Br replace aryl, phenyl replace aryl; The five-membered ring of described O, N or S or the heteroaryl of hexatomic ring refer to pyridine radicals, furans or thienyl.

3. catalyst as claimed in claim 1, it is characterized in that, described catalyst has following structural formula:

Wherein, described R, R ¹, R ²with described in claim 1.

4. catalyst as claimed in claim 1, is characterized in that described catalyst has following structural formula:

5. a preparation method for catalyst as claimed in claim 1, is characterized in that described catalyst is obtained according to following two preparation were establisheds respectively by chiral diol:

(1) azido reaction: under in organic solvent with 0 DEG C ~ room temperature, the reaction of chiral diol, sodium azide, trifluoroacetic acid and TFMS obtains product azide in 0.1 ~ 1 hour; Mol ratio 1:2 ~ 5:5 ~ 10:10 ~ 20 of described chiral diol, sodium azide, trifluoroacetic acid and TFMS;

(2) reduction reaction: in 0 DEG C and organic solvent, the product azide that (1) step obtains and Lithium Aluminium Hydride or sodium borohydride react according to mol ratio 1:4 ~ 10 chiral diamine that 1 ~ 6 hour obtains tartaric acid skeleton or cyclohexanediamine skeleton;

(3) phosphonitrile salt precursor is prepared in spirocyclization reaction: in organic solvent with under reflux temperature, the tartaric acid skeleton that (2) step obtains or the chiral diamine of cyclohexanediamine skeleton, to react according to mol ratio 2:2 ~ 5:3 ~ 20 with phosphorus pentachloride, triethylamine and within 1 ~ 10 hour, obtain phosphonitrile salt precursor compound;

(4) phosphonitrile super basic catalyst is prepared in quaternization: by step (3) in the phosphonitrile salt precursor compound that obtains be dissolved in organic solvent, be neutralized to neutrality with the tetrahydrofuran solution of saturated monovalent metal hydroxide aqueous solution or potassium tert-butoxide, obtain chirality phosphonitrile base catalyst;

Wherein, R, R ' or n as claimed in claim 1.

6. the preparation method of catalyst as claimed in claim 5, it is characterized in that the reaction of step (1) is that chiral diol, sodium azide, trifluoroacetic acid and TFMS are respectively 1:2 ~ 5:5 ~ 10 according to mol ratio: stir, cooling, add the mixed acid of mol ratio 1:1 ~ 1:10 TFMS and trifluoroacetic acid, be warming up to room temperature, continue reaction 10 ~ 40 minutes; Described azide is sodium azide, potassium azide or diphenyl phosphate azide.

7. the preparation method of catalyst as claimed in claim 5, it is characterized in that described step (1), (2), (3) or the organic solvent described in (4) are chloroform, trichloroethanes, toluene, oxolane, benzinum, ether, carrene, or DMF.

8. the preparation method of catalyst as claimed in claim 5, is characterized in that described step (1), (2) or (3) reaction frozen water quencher reaction.

9. the preparation method of catalyst as claimed in claim 5, is characterized in that the product of step (1) is through ammonia neutralization, organic solvent extraction, and washing is dry, filters, concentrated or recrystallization purifying process; Step (2) product passes through and filters, drying, ethyl acetate organic solvent dissolution, saturated common salt water washing, concentrated or recrystallization purifying process; Step (3) is through filtering, concentrated, recrystallization or column chromatography purification process; Step (4) product is through separatory, dry, concentrated, recrystallization purifying process.

10. chirality phosphonitrile base catalyst as claimed in claim 1 is used for the active halogenation of nucleophile, a catalyst for the Michael addition reaction of dicarbonyl compound, or is used for allylation reaction with palladium compound complexing as chiral metal catalyst.