CN101220048B - Method for preparing pinane diol ester under ZnCl2 catalysis - Google Patents
Method for preparing pinane diol ester under ZnCl2 catalysis Download PDFInfo
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- -1 pinane diol ester Chemical class 0.000 title claims description 19
- 238000006555 catalytic reaction Methods 0.000 title claims description 4
- 238000000034 method Methods 0.000 title abstract description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 title abstract description 6
- 239000011592 zinc chloride Substances 0.000 title abstract description 4
- 235000005074 zinc chloride Nutrition 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 46
- 238000002360 preparation method Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000007818 Grignard reagent Substances 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 7
- 150000004795 grignard reagents Chemical class 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052756 noble gas Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- ZYBFWPARLOUPMV-UHFFFAOYSA-L dichlorozinc;ethoxyethane Chemical compound [Cl-].[Cl-].[Zn+2].CCOCC ZYBFWPARLOUPMV-UHFFFAOYSA-L 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 150000001491 aromatic compounds Chemical class 0.000 abstract description 2
- MOILFCKRQFQVFS-BDNRQGISSA-N (1r,3s,4r,5r)-4,6,6-trimethylbicyclo[3.1.1]heptane-3,4-diol Chemical class C1[C@@H]2C(C)(C)[C@H]1C[C@H](O)[C@@]2(O)C MOILFCKRQFQVFS-BDNRQGISSA-N 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- GMSWPHLERKDKGU-UHFFFAOYSA-N C1(=CC=CC=C1)CC(C[B])Cl Chemical compound C1(=CC=CC=C1)CC(C[B])Cl GMSWPHLERKDKGU-UHFFFAOYSA-N 0.000 description 2
- JPYOFUMXHUMBGL-UHFFFAOYSA-N CCCC(C[B])Cl Chemical compound CCCC(C[B])Cl JPYOFUMXHUMBGL-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000006219 Matteson homologation reaction Methods 0.000 description 1
- 208000034578 Multiple myelomas Diseases 0.000 description 1
- 206010035226 Plasma cell myeloma Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- GXJABQQUPOEUTA-RDJZCZTQSA-N bortezomib Chemical compound C([C@@H](C(=O)N[C@@H](CC(C)C)B(O)O)NC(=O)C=1N=CC=NC=1)C1=CC=CC=C1 GXJABQQUPOEUTA-RDJZCZTQSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- SCEZYJKGDJPHQO-UHFFFAOYSA-M magnesium;methanidylbenzene;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C1=CC=CC=C1 SCEZYJKGDJPHQO-UHFFFAOYSA-M 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229940099039 velcade Drugs 0.000 description 1
Abstract
The invention relates to a method for synthesizing chiral pinane diol esters under the existence of ZnCl2. The following reaction route is adopted; wherein R is a fatty compound or an aromatic compound; X is halogen. The method has the advantages of simple operation, reasonable reaction route, low production cost and high product quality, high overall yield reaching over 90 percent, no pollution to the environment and being able to be used in industrial production.
Description
Technical field
The present invention relates to a kind of at ZnCl
2There is the method for synthesis of chiral pinane diol ester down, belongs to the field of chemical synthesis.
Background information
Containing boron compound is organic Lewis acid of one type of gentleness, and character more stable and easy handling and processing are one type of important organic synthesis intermediates.Simultaneously and since this compounds to human toxicity very little with and eventual degradation become eco-friendly boric acid compound, so this compounds is considered to " green product ".Because the organic boronic compound is easy to form the oligomerization boron trioxide, therefore, in actual synthetic work, usually uses organic boric acid ester as reaction intermediate.In all boric acid esters, the pinane diol ester of chirality has very important use valency and since its molecule in have four chiral carbon and steric hindrance bigger, can be as chiral induction reagent in asymmetric synthesis.This compound is important intermediate (the US patent of synthetic anti-recurrence property myelomatosis Velcade
; 1998; 5; 780,454).
In U.S. Pat 4,525, the compound method of pinane diol ester has been discussed in 309.The inventor has adopted following method synthesising target compound:
In this route, the dihalo metal reagent that adopts when generating midbody (II) by raw material (I) mainly refers to LiCHCl
2, this compound is by CH under-100 ℃
2Cl
2With n-C
4H
9Li reacts generation, and this metal reagent is to empty G&W and sensitivity thereof, so in transfer process, require very strict and harsh.When in use mesosome (II) generates product (III), adopted the very easily solid ZnCl of suction
2Powder has been introduced moisture in the feasible reaction, has decomposed the LiCHCl of part
2, cause the productive rate of product (III) lower.And when aftertreatment because the method that adopts is improper, the processing difficulty relatively that makes reaction exerts a certain influence to product gas purity.
Summary of the invention
The invention provides the novel method and the variation route of a kind of synthetic (III), be used to prepare the pinane diol ester (III) of chirality.
For achieving the above object, the present invention takes following reaction scheme:
R is fats compound or aromatic compounds, and X is a halogen.
The preparation method is: with the Grignard reagent RMgX and raw material (1) the reaction generation midbody (2) that are easy to prepare and preserve, (2) are again at the anhydrous ZnCl of Lewis acid
2Catalysis generate down the pinane diol ester (III) of chirality.
The preparation of raw material among the present invention (1) is referring to below with reference to document:
（1）Rathke,?M.?W.;?Chao,?E.;?Wu,?G.?J.?Organomet.?Chem.?1976,?122,?145-149.
（2）Elgendy,?S.;?Deadman,?J.;?Patel,?G.;?Green,?D.;?Chion,?N.;?Goodwin,?C.?A.;?Scully,?M.?F.;?Kakkar,?V.?V.;?Claeson,?G.?Tetrahedron?Lett.?1992,?33,?4209-4212.
（3）Matteson,?D.?S.?Chem.?Rev.?1989,?89,?1535-1551.
The reaction conditions of synthetic (III) is:
When (1) preparing Grignard reagent RMgX, the mol ratio of metal M g and halides RX is 1:1 ~ 2, is preferably 1:1.2 ~ 1.5.Solvent is benzene, toluene, ether, THF, dioxane.Optimum solvent is an ether.
(2) under the noble gas protection, grignard reagent RMgX is added drop-wise under-40 ~-100 ℃ by in the compound of dissolution with solvents (1), carries out next step operation again.
Said noble gas is N
2, Ar;
Said solvent is benzene, toluene, sherwood oil, ether, THF, dioxane, and preferred solvent is ether and THF, and most preferred solvent is an ether;
The optimum temps of reaction is-60 ~-78 ℃.
(3) after Grignard reagent dropwises, add the anhydrous ZnCl of catalyzer at once
2, make the reaction nature slowly rise to room temperature then, under the noble gas protection, continue reaction.The general reaction times is 8 ~ 30 hours, and optimum reacting time is 15 ~ 24 hours.After reaction finishes, the undissolved ZnCl of filtering
2, in filtrating, add ZnCl
2Remove liquid, separatory, organic phase is used the saturated common salt water washing again.Anhydrous Na
2SO
4Dry.Boil off solvent under the vacuum, promptly get product.
The ZnCl of indication among the present invention
2Remove liquid and be meant that mass concentration is 10 ~ 40% NH
4Cl, (NH
4)
2SO
4, NH
4NO
3Deng the strong acid weak base salts solution.
The inventor finds through experiment back repeatedly, and through facts have proved, in this reaction, catalyzer ZnCl
2Quality be the key factor of decision reaction yield and quality product.ZnCl
2Under the effect of vacuum and dewatering agent, can dewater at a lower temperature.Usually, at normal pressure with greater than 180 ℃ of ZnCl that dewater and make down
2Be lead, be blocks of solid, be unfavorable under reaction conditions dissolving, cause product yield low, poor product quality, and during aftertreatment difficulty remove.
The ZnCl of the low temperature dewatering of indication in the invention
2, being meant temperature between 40～200 ℃, vacuum tightness is at 0.01～100mmHg, and the ZnCl that under the condition that dehydration system exists, prepares
2, dehydration was accomplished at 1～20 hour.
Dehydration system is meant Vanadium Pentoxide in FLAKES, the vitriol oil, SPA, molecular sieve, KOH or discolour silica gel etc.
The inventor also finds through a large amount of experiments, like the anhydrous ZnCl that will very easily absorb water
2Be prepared into its diethyl ether solution, utilize same Dropping feeder that this solution is added in the reactor drum after Grignard reagent adds in reaction, not only avoided direct adding solid ZnCl
2This difficult problem of meeting suction, and the yield of reaction also can improve.
The invention has the beneficial effects as follows easy and simple to handlely, reaction process is reasonable, and production cost is low, good product quality, and total recovery is up to more than 90%.Environmentally safe can be used for suitability for industrialized production.
Embodiment
Below in conjunction with embodiment the present invention is further specified:
Embodiment 1 low temperature dewatering ZnCl
2Preparation
With 500g technical grade zinc chloride (5mmHg) under vacuum, be heated to 150 ℃, under mechanical stirring, be incubated 10 hours continuously, steam the moisture that comes and absorb with an amount of Vanadium Pentoxide in FLAKES, obtain about 480g white powdery Zinc Chloride Anhydrous.
The preparation of embodiment 2 Grignard reagent tertiary butyl bromination magnesium
In the strict dry 250mL three-necked bottle of crossing, add and stir magneton, load onto prolong and constant pressure funnel, at the device calcium chloride tube suitable for reading of prolong.Pack in the reaction flask 3.1g (0.13mol) magnesium chips, 15ml anhydrous diethyl ether and a granule crystalline flake of iodine.In tap funnel, mix 16.2ml (0.16mol) tert-bromo butane and 15ml ether.Earlier in bottle, splash into about 5ml mixed solution, bath temperature is heated to be 30 ℃.After several minutes, solution is slight boiling condition, and the color of iodine disappears, and solution becomes grey.It is comparatively violent just to have begun reaction, available ice block cooling.After question response relaxes, add the 25ml anhydrous diethyl ether from the prolong upper end, begin to stir, and slowly splash into the diethyl ether solution of remaining tert-bromo butane, the control rate of addition makes reaction solution be slight boiling condition.After dropwising, treat that most of magnesium chips disappears after, reflux in water-bath makes remaining magnesium chips effect complete.Reaction system is slowly cooled off, subsequent use.
The preparation of embodiment 3 Grignard reagent benzylmagnesium chlorides
Middle port device for mechanical at the strict dry 1.0L three-necked bottle of crossing stirs, and two other side mouth installs constant pressure funnel and prolong respectively, the device calcium chloride tube suitable for reading of prolong.In reaction flask, add 150mL exsiccant anhydrous diethyl ether in advance, add the magnesium chips of 11.2g (0.46mol) then.Reaction unit is placed in 20～23 ℃ the water bath.75.9g (0.60mol) benzyl chloride and 350mL exsiccant ether are blended in the tap funnel, and the sub-fraction mixed solution is splashed into initiation reaction in the reaction flask.React Once you begin, solution colour becomes grey black, slowly starts this moment to stir.Slowly add remaining mixed solution, make reaction keep little boiling, about 10h of dropping time altogether.Cooling is transferred to reaction solution in the exsiccant bottle and to be sealed, and is subsequent use.
Embodiment 4 4-methyl-2-chloro-butyl boron dihydroxide-australene alkane diol ester
The molecular structural formula of 4-methyl-2-chloro-butyl boron dihydroxide-australene alkane diol ester is:
Its concrete method for making is following:
In the there-necked flask of 150ml, add dichloromethyl boric acid-australene alkane diol ester 7.89g (30mmol) with the 20mL ether dissolution, stir under the room temperature.Feed exsiccant nitrogen, and system is cooled to-78 ℃, slowly drip the diethyl ether solution 50mL (30mmol) of the tertiary butyl bromination magnesium that makes then, after dropwising, disposable adding is dissolved with the exsiccant ZnCl of 2.45g (18mmol)
2The diethyl ether solution 15ml of powder art.Naturally rise to room temperature, continue at room temperature to stir the 18h afterreaction and finish.Remove by filter ZnCl
2And the MgBr of reaction generation
2, filtrating is used 20% NH respectively
4Cl solution and saturated NaCl solution washing, organic phase is used anhydrous sodium sulfate drying.Remove solvent under reduced pressure.Concentrate back column chromatography for separation (ETHYLE ACETATE: sherwood oil=1: 200) get colourless liquid 7.88g, yield 92.5%.
Embodiment 5 3-phenyl-2-chloro-propyl boron dihydroxide-australene alkane diol ester
The molecular structural formula of 3-phenyl-2-chloro-propyl boron dihydroxide-australene alkane diol ester is:
The preparation method is following:
In the there-necked flask of 500ml, add dichloromethyl boric acid-australene alkane diol ester 35.5g (135mmol) with the 100mL ether dissolution, stir under the room temperature.Feed exsiccant nitrogen, and system is cooled to-60 ℃, slowly drip the diethyl ether solution 200mL (135mmol) of the benzylmagnesium chloride that makes then, after dropwising, disposable adding is dissolved with the exsiccant ZnCl of 11.03g (81mmol)
2The diethyl ether solution 80ml of powder.Naturally rise to room temperature, continue stirred overnight reaction at room temperature.Remove by filter ZnCl
2And the MgCl of reaction generation
2, filtrating is used 15% NH respectively
4NO
3Solution and saturated NaCl solution washing, organic phase is used anhydrous sodium sulfate drying.Remove solvent under reduced pressure.Concentrate back column chromatography for separation (ETHYLE ACETATE: sherwood oil=1: 120) get colourless liquid 40.73g, yield 94.7%.
Claims (10)
1. the preparation method of a pinane diol ester, its reaction scheme is following:
A in noble gas protection down, is dissolved in Grignard reagent RMgX in the solvent and raw material 1 reaction generation midbody 2, and wherein R is aliphatics substituting group or aromatic substituents, and X is a halogen;
B, midbody 2 are again at anhydrous ZnCl
2Diethyl ether solution catalysis generate down the pinane diol ester III of chirality.
2. preparation method according to claim 1 is characterized in that the described solvent of step a is benzene, toluene, sherwood oil, ether, THF or dioxane.
3. preparation method according to claim 2 is characterized in that the further preferred ether of the described solvent of step a.
4. preparation method according to claim 1 is characterized in that the said noble gas of step a is N
2Or Ar.
5. preparation method according to claim 1 is characterized in that step a temperature of reaction is-40～-100 ℃.
6. preparation method according to claim 1 is characterized in that the said reaction of step b slowly rises to room temperature naturally.
7. preparation method according to claim 1, the reaction times that it is characterized in that step b is 8 ~ 30 hours.
8. preparation method according to claim 7 is characterized in that preferred 15 ~ 24 hours of reaction times of step b.
9. preparation method according to claim 1, after the reaction that it is characterized in that step b finishes, the undissolved ZnCl of filtering
2, in filtrating, add ZnCl again
2Remove liquid.
10. preparation method according to claim 9 is characterized in that said ZnCl
2Removing liquid is that mass concentration is 10 ~ 40% NH
4Cl, (NH
4)
2SO
4Or NH
4NO
3Solution.
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|---|---|---|---|
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|---|---|---|---|
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4525309A (en) * | 1983-03-15 | 1985-06-25 | Washington State University Research Foundation, Inc. | Lewis acid catalysis of the homologation of boronic esters with haloalkylmetal reagents |
| US5780454A (en) * | 1994-10-28 | 1998-07-14 | Proscript, Inc. | Boronic ester and acid compounds |
-
2007
- 2007-12-14 CN CN 200710191693 patent/CN101220048B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4525309A (en) * | 1983-03-15 | 1985-06-25 | Washington State University Research Foundation, Inc. | Lewis acid catalysis of the homologation of boronic esters with haloalkylmetal reagents |
| US5780454A (en) * | 1994-10-28 | 1998-07-14 | Proscript, Inc. | Boronic ester and acid compounds |
Non-Patent Citations (3)
| Title |
|---|
| Donald S. Matteson et al..99% Chirally Selective Syntheses via Pinanediol Boronic Esters:Insect Pheromones, Diols, and an Amino Alcohol.《J. Am. Chem. Soc》.1986,第108卷(第4期),第810-819页. * |
| Donald S. Matteson et al..Asymmetric synthesis of 1-acyl-3,4-disubstituted pyrrolidine-2-boronic acid derivatives.《Tetrahedron:Asymmetry》.1998,第9卷(第14期),2424,2427-2428页. * |
| DonaldS.Mattesonetal..Asymmetricsynthesisof1-acyl-3 4-disubstituted pyrrolidine-2-boronic acid derivatives.《Tetrahedron:Asymmetry》.1998 |
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|---|---|
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