CN105688987A - Novel chiral phosphoric acid catalyst as well as synthetic method and application thereof - Google Patents

Novel chiral phosphoric acid catalyst as well as synthetic method and application thereof Download PDF

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CN105688987A
CN105688987A CN201610135778.2A CN201610135778A CN105688987A CN 105688987 A CN105688987 A CN 105688987A CN 201610135778 A CN201610135778 A CN 201610135778A CN 105688987 A CN105688987 A CN 105688987A
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dinaphthalene
phosphoric acid
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程旭
王震
谷芳军
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Nanjing University
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    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0257—Phosphorus acids or phosphorus acid esters
    • B01J31/0259—Phosphorus acids or phosphorus acid esters comprising phosphorous acid (-ester) groups ((RO)P(OR')2) or the isomeric phosphonic acid (-ester) groups (R(R'O)2P=O), i.e. R= C, R'= C, H
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    • C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
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    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
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Abstract

The invention discloses a novel chiral phosphoric acid catalyst as well as a synthetic method and an application thereof. A 3,3'-bis(1,2,3,4,5,6,7,8-octahydroanthracence-9yl)2,2'-hydroxy phosphoryl dioxy-1,1'-dinaphthalene chiral phosphoric acid catalyst, namely, DGW-PA*, is prepared by introducing hydroxy phosphoryl dioxy into the 3,3' position of a dinaphthalene framework, in an asymmetry addition reaction of aldehyde by amide, the catalyst has efficient catalytic performance and stereoselectivity, and a hemiaminal compound can be obtained at the high yield. The catalyst and a key intermediate of the catalyst have the structural formula shown in the specification, wherein X is any one of a methoxy group, a hydroxyl group and hydroxy phosphoryl dioxy, and the catalyst and the key intermediate of the catalyst contain a raceme, an S configuration and an R configuration.

Description

A kind of novel chiral phosphoric acid catalyst and synthetic method thereof and application
Technical field
The invention belongs to the organic synthesis of Chemical Engineering Technology and application, be specifically related to a kind of novel chiral phosphoric acid catalyst and synthetic method thereof and application。
Background technology
Asymmetry catalysis is the study hotspot of current synthetic organic chemical art, and it can be divided three classes according to catalyst classification: 1) metal complex catalyst；2) organic molecule catalyst；3) enzyme。Wherein organic molecule catalyst is without metal, and environment and biology is friendly, and in catalytic reaction, the impact by impurity is little, it is possible to achieve specific catalytic reaction。In organic molecule catalyst, chiral phosphoric acid catalyst is a class proton acid catalyst, in the nucleopilic reagent additive reaction to imines, chiral ion catalysis activity and stereo selectivity to all showing excellence in catalysis。In chiral phosphoric acid Catalyst Design synthesizes, 3, the substituent group of 3 ' positions controls most important for the stereo selectivity of reaction, different substituents can realize different stereo selectivity control abilities, patent WO2004096753A1 such as Japanese Toagosei Co., Ltd application in 2004, cover multiple 3,3 ' substituted radicals, wherein famous triisopropyl phenyl substituent group, it is called for short TRIP, in the reaction of a lot of chiral phosphoric acid catalyst, it is thus achieved that well application (ChemRev.2007,107,5744)。And for example 2005, the patent 2005070875A1 of STOL company of Japan application, the chiral phosphoric acid that application 9-anthryl replaces also obtains good application, is listed as two big efficiently chiral catalysts (Chem.Rev.2014,114,9047-9153) with TRIP catalyst。2013, California, USA Berkeley University applied for a patent WO2013096971A1, protected the chiral phosphoric acid catalyst that thricyclohexyl phenyl replaces, the well application (NatureChem.2012,4,603) obtained in phase transfer catalyst。
In these successful chiral phosphoric acid catalyst, 3, the substituted radical of 3 ' positions is different, different reactions has different effects, at amide in the reaction of the asymmetric addition of aldehyde, there is presently no can the catalyst of highly-solid selectively can the acquisition hemiacetal amines of high yield, it is therefore desirable to develop new efficient chirality phosphoric acid catalyst。
Summary of the invention
It is an object of the invention to, a kind of novel chiral phosphoric acid catalyst and synthetic method thereof and application are provided, making at amide in the reaction of the asymmetric addition of aldehyde, this kind of catalyst has efficient catalytic performance and stereo selectivity, it is possible to the acquisition hemiacetal amines of high yield。
For achieving the above object, the present invention adopts the following technical scheme that
A kind of novel chiral phosphoric acid catalyst in the present invention, this catalyst and key intermediate thereof are structured with formula:
Wherein X is methoxyl group, hydroxyl and in hydroxyl phosphinylidyne dioxy base any one。
In the present invention, described key intermediate can be racemic 3,3 '-(1,2,3,4,5,6,7,8-octahydro anthracene-9 bases)-2,2 '-dialkoxy-1,1 '-dinaphthalene, (S)-(1,2,3,4,5,6,7,8-octahydro anthracene-9 bases)-2,2 '-dialkoxy-3,3 '-1,1 '-dinaphthalene, (R)-(1,2,3,4,5,6,7,8-octahydro anthracene-9 base)-2,2 '-dialkoxy-3,3 '-1,1 '-dinaphthalene, wherein the part of alkyl can be methyl or methoxyl methyl, and structural formula is as follows respectively:
In the present invention, described key intermediate can also be racemic 2,2 '-dihydroxy-3,3 '-(1,2,3,4,5,6,7,8-octahydro anthracene-9 bases), (S)-2,2 '-dihydroxy-3,3 '-(1,2,3,4,5,6,7,8-octahydro anthracene-9 bases), (R)-2,2 '-dihydroxy-3,3 '-(1,2,3,4,5,6,7,8-octahydro anthracene-9 bases), and structural formula is as follows respectively:
In the present invention, described catalyst is racemic 2,2 '-hydroxyl phosphinylidyne dioxy base-3,3 '-(1,2,3,4,5,6,7,8-octahydro anthracene-9 bases)-1,1 '-dinaphthalene, (S)-2,2 '-hydroxyl phosphinylidyne dioxy base-3,3 '-(1,2,3,4,5,6,7,8-octahydro anthracene-9 bases)-1,1 '-dinaphthalene, (R)-2,2 '-hydroxyl phosphinylidyne dioxy base-3,3 '-(1,2,3,4,5,6,7,8-octahydro anthracene-9 base)-1,1 '-dinaphthalene, structural formula is as follows respectively:
And this kind of catalyst cartridge is called DGW-PA*。
The synthetic method of a kind of novel chiral phosphoric acid catalyst in the present invention, it concretely comprises the following steps: 1) with the 1,2 of 2～8 equivalents, 3,4,5,6,7, the 8-bromo-anthracenes of octahydro-9-are raw material, react with the magnesium metal of 2～80 equivalents, generate 1,2,3,4,5, the Grignard reagent of 6,7, the 8-bromo-anthracenes of octahydro-9-。By this Grignard reagent and 3, the 3 '-two bromo-2 of 1 equivalent, 2 '-dialkoxy-1, there is coupling reaction in 1 '-dinaphthalene, generate key intermediate 3,3 '-two (1 under the catalysis of two (triphenylphosphine)-Nickel Chlorides, 2,3,4,5,6,7,8-octahydro anthracene-9 bases)-2,2 '-dialkoxy-1,1 '-dinaphthalene。Wherein, reaction temperature is 25 DEG C～60 DEG C, and solvent is the organic solvents such as ether, oxolane。
2) with the Boron tribromide of 2～8 equivalents and the key intermediate 3,3 '-two (1,2,3 in step (1), 4,5,6,7,8-octahydro anthracene-9 base)-2,2 '-dialkoxy-1,1 '-dinaphthalene reacts, and elimination methyl generates another key intermediate 3,3 '-two (1,2,3,4,5,6,7,8-octahydro anthracene-9 base)-2,2 '-dihydroxy-1,1 '-dinaphthalene。Wherein, reaction temperature is-80 DEG C～25 DEG C, and solvent is the organic solvents such as dichloromethane。
3) with the phosphorus oxychloride of 2～8 equivalents and key intermediate 3,3 '-two (1,2,3 in step (2), 4,5,6,7,8-octahydro anthracene-9 base)-2,2 '-dihydroxy-1,1 '-dinaphthalene reacts, and reactant mixture directly reacts with the water of 1～100 equivalent, generate 3,3 '-two (1,2,3,4,5,6,7,8-octahydro anthracene-9 base) 2,2 '-hydroxyl phosphinylidyne two Oxy-1,1 '-dinaphthalene chiral phosphoric acid catalyst (i.e. DGW-PA*)。Wherein, reaction temperature is 0 DEG C～110 DEG C, and solvent is the organic solvents such as pyridine, triethylamine。
The application of a kind of novel chiral phosphoric acid catalyst in the present invention, described DGW-PA* is used for the stereo selectivity addition to aldehyde of the catalysis amide as catalyst in appropriate solvent, and its catalytic process is as follows:
Preferably, described appropriate solvent is the ether solvent of C4-C6, or the mixed solvent of ether and other organic solvent composition, and catalyst amount is 1%～10%, and reaction temperature is 0～60 DEG C, and the response time is 4 hours～4 days。
The beneficial effects of the present invention is, chiral phosphoric acid catalyst this kind novel, its synthetic method has that synthetic route is succinct, reaction process is stable, environmental protection and economy, the advantage such as with low cost, its synthesis has been broken at amide in the reaction of the asymmetric addition of aldehyde, there is presently no can highly-solid selectively catalyst can high yield obtain hemiacetal amines present situation, have broad application prospects。
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further described below。
A kind of synthetic method of novel chiral phosphoric acid catalyst, it specifically includes following steps:
1) 3,3 '-two (1,2,3,4,5,6,7,8-octahydro anthracene-9 base)-2,2 '-dialkoxy-1, the preparation of 1 '-dinaphthalene: under nitrogen atmosphere, by 1,2,3,4,5,6,7, the 8-bromo-anthracene (6.36mg of octahydro-9-, 25mL diethyl ether solution 24mmol) instills in the 25mL ether suspension of magnesium chips (7.20g, 300mmol), is simultaneously heated to 55 DEG C of initiation reactions。After reaction occurs, reaction temperature is kept to drip the diethyl ether solution of remaining 1,2,3,4,5,6,7, the 8-bromo-anthracene of octahydro-9-for about 40 DEG C temperature controls with water-bath。After dripping, reflux 1.5 hours, obtain milky white solution。Under stirring, this solution is instilled another and fills 3,3 '-two bromo-2,2 '-dialkoxy-1, in the reaction bulb of 1 '-dinaphthalene (1.4g, 3mmol), two (triphenylphosphine)-Nickel Chlorides (200mg, 0.3mmol) and 25mL ether。After dripping, temperature control 40 DEG C reacts 12 hours。Then, under ice bath, 1N hydrochloric acid (20mL) cancellation reaction is added。Extracting with ether, organic facies saturated common salt water washing collection obtained, anhydrous sodium sulfate dries, and filters, and reduce pressure precipitation, obtains 3,3 '-two (1,2,3,4,5,6,7,8-octahydro anthracene-9 bases)-2,2 '-dialkoxy-1,1 '-dinaphthalene (yellow oily liquid 1.8g)。Product is used directly for next step reaction, it is not necessary to further purification。Yield 90%。
2) 3,3 '-two (1,2,3,4,5,6,7,8-octahydro anthracene-9 bases)-2,2 '-dihydroxy-1, the preparation of 1 '-dinaphthalene: by step 1) obtain 3,3 '-two (1,2,3,4,5,6,7,8-octahydro anthracene-9 base)-2,2 '-dialkoxy-1,1 '-dinaphthalene (2.0g, 0.3mmol) it is dissolved in 75mL dichloromethane, it is cooled to 0 DEG C, then dropwise drips Boron tribromide (2mL, 21mmol), dropwising and stir 24 hours under rear room temperature, add water cancellation。With dichloromethane extraction, saturated common salt water washing, anhydrous sodium sulfate dries, and decompression precipitation obtains yellow solid。3 are obtained with petrol ether/ethyl acetate (95:5) column chromatography, 3 '-two (1,2,3,4,5,6,7,8-octahydro anthracene-9 bases)-2,2 '-dihydroxy-1,1 '-dinaphthalene (yellow solid 1.8g), yield 95%。
1HNMR (400MHz, CDCl3) δ 7.89 (d, J=7.9Hz, 2H), 7.74 (s, 2H), 7.41 (t, J=6.9Hz, 2H), 7.34 (t, J=7.1Hz, 2H), 7.26 (d, 2H), 6.95 (s, 2H), 5.08 (s, 2H), 2.90 2.19 (m, 16H), 1.89 1.62 (m, 16H).
13CNMR(400MHz,CDCl3)δ149.73,135.63,134.80,134.71,133.49,133.46,133.37,130.33,130.25,129.59,129.45,128.17,126.65,124.86,123.74,113.05,29.74,29.71,27.81,27.61,23.55,23.52,23.04,22.96.
HRMS,ESI(M+Na+),calc.for(C96H92O4Na):1331.6888,found:1331.6836.
Fusing point: 151.3 DEG C-156.8 DEG C
3) 3,3 '-two (1,2,3,4,5,6,7,8-octahydro anthracene-9 bases) 2,2 '-hydroxyl phosphinylidyne two Oxy-1, the preparation of 1 '-dinaphthalene (DGW-PA*): under nitrogen atmosphere, phosphorus oxychloride (1.4mL, 15mmol) is instilled 3,3 '-two (1,2,3,4,5,6,7,8-octahydro anthracene-9 bases)-2,2 '-dihydroxy-1, in the 1mL pyridine solution of 1 '-dinaphthalene (3.3g, 5mmol), heats to 110 DEG C of reactions 14 hours。Being cooled to room temperature, add 1.1mL water, heating, to 110 DEG C, continues reaction 3 hours。Being cooled to room temperature, add 50mL dichloromethane, organic facies 1N salt acid elution (3 × 50mL), anhydrous sodium sulfate dries, and reduce pressure precipitation。The brown solid petroleum ether that will obtain: ethyl acetate (1:1) column chromatography, obtains DGW-PA* (white solid 2.8g)。Yield 80%。
1HNMR (400MHz, CDCl3) δ 7.91 (d, J=8.2Hz, 2H), 7.77 (s, 2H), 7.51 (t, J=7.4Hz, 2H), 7.40 (d, J=8.4Hz, 2H), 7.37 7.30 (m, 2H), 6.77 (s, 2H), 2.73 2.15 (m, 16H), 1.70 1.30 (m, 16H).
13CNMR(400MHz,CDCl3)δ145.38,145.28,135.73,134.34,133.87,133.52,133.48,132.81,131.99,131.66,131.61,129.62,128.17,127.24,126.18,125.59,122.33,77.35,77.24,77.03,76.71,48.49,29.74,29.54,28.57,27.08,23.37,23.32,22.80,22.77,14.13.
HRMS,ESI(M+Na+),calc.for(C48H45O4PNa):739.2948,found:739.2912
Fusing point: 278.2 DEG C-282.3 DEG C
DGW-PA* obtained by above-mentioned steps is used for the stereo selectivity additive reaction to aldehyde of the catalysis amide, in the present embodiment, for the reaction of Benzoylamide and glyoxylic acid ethyl ester。Its course of reaction is as follows:
Glyoxylic acid ethyl ester (toluene solution of 0.2mL, 1mmol, 50%) is instilled in the 7mL diethyl ether solution of Benzoylamide (121mg, 1mmol) and DGW-PA* (72mg, 0.1mmol), react 24 hours under room temperature。The white slurry liquid obtained is filtered, with a small amount of cold washed with diethylether, obtains white solid 130mg, yield 60%。Ee%=98.5%。Experimental results is shown in table 1 below
Table 1: the amide experimental result to the stereo selectivity additive reaction of aldehyde

Claims (7)

1. chiral phosphoric acid catalyst one kind novel, it is characterised in that this catalyst and key intermediate thereof are structured with formula:
Wherein, X is methoxyl group, hydroxyl and in hydroxyl phosphinylidyne dioxy base any one。
2. a kind of novel chiral phosphoric acid catalyst according to claim 1, it is characterized in that, described key intermediate is racemic 3, 3 '-(1, 2, 3, 4, 5, 6, 7, 8-octahydro anthracene-9 base)-2, 2 '-dialkoxy-1, 1 '-dinaphthalene, (S)-(1, 2, 3, 4, 5, 6, 7, 8-octahydro anthracene-9 base)-2, 2 '-dialkoxy-3, 3 '-1, 1 '-dinaphthalene, (R)-(1, 2, 3, 4, 5, 6, 7, 8-octahydro anthracene-9 base)-2, 2 '-dialkoxy-3, 3 '-1, 1 '-dinaphthalene, wherein the part of alkyl can be methyl or methoxyl methyl, and structural formula is as follows respectively:
3. a kind of novel chiral phosphoric acid catalyst according to claim 1, it is characterised in that described key intermediate is racemic 2,2 '-dihydroxy-3,3 '-(1,2,3,4,5,6,7,8-octahydro anthracene-9 bases), (S)-2,2 '-dihydroxy-3,3 '-(1,2,3,4,5,6,7,8-octahydro anthracene-9 bases), (R)-2,2 '-dihydroxy-3,3 '-(1,2,3,4,5,6,7,8-octahydro anthracene-9 bases), and structural formula is as follows respectively:
4. a kind of novel chiral phosphoric acid catalyst according to claim 1, it is characterised in that described catalyst is racemic 2,2 '-hydroxyl phosphinylidyne dioxy base-3,3 '-(1,2,3,4,5,6,7,8-octahydro anthracene-9 bases)-1,1 '-dinaphthalene, (S)-2,2 '-hydroxyl phosphinylidyne dioxy base-3,3 '-(1,2,3,4,5,6,7,8-octahydro anthracene-9 bases)-1,1 '-dinaphthalene, (R)-2,2 '-hydroxyl phosphinylidyne dioxy base-3,3 '-(1,2,3,4,5,6,7,8-octahydro anthracene-9 base)-1,1 '-dinaphthalene, structural formula is as follows respectively:
5. the synthetic method of a novel chiral phosphoric acid catalyst as claimed in claim 4, it is characterised in that it concretely comprises the following steps: from 3,3 '-two bromo-2,2 '-dialkoxy-1,1 '-dinaphthalene is initiation material, through with 1,2,3,4,5,6,7, the Grignard reagent coupling of 8-octahydro-9-bromine anthracene, obtains key intermediate 3, and 3 '-two (1,2,3,4,5,6,7,8-octahydro anthracene-9 bases)-2,2 '-dialkoxy-1,1 '-dinaphthalene；Another key intermediate 3,3 '-two (1,2,3,4,5,6,7,8-octahydro anthracene-9 base)-2,2 is obtained through elimination methyl '-dihydroxy-1,1 '-dinaphthalene；Phosphorylated obtain end product 2,2 '-hydroxyl phosphinylidyne dioxy base-3,3 '-(1,2,3,4,5,6,7,8-octahydro anthracene-9 base)-1,1 '-dinaphthalene。
6. the application of a novel chiral phosphoric acid catalyst as claimed in claim 4, it is characterised in that described catalyst is used for the stereo selectivity addition to aldehyde of the catalysis amide as catalyst in appropriate solvent, and its catalytic process is as follows:
7. the application of a kind of novel chiral phosphoric acid catalyst according to claim 6, it is characterized in that, described appropriate solvent is the ether solvent of C4-C6, or the mixed solvent of ether and other organic solvent composition, catalyst amount is 1mol%～10mol%, reaction temperature is 0～40 DEG C, and the response time is 4 hours～4 days。
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CN109651135A (en) * 2018-12-13 2019-04-19 山东师范大学 A kind of preparation method and application of chirality Zr-MOF catalyst
CN112299962A (en) * 2020-10-19 2021-02-02 山东新和成药业有限公司 Synthesis method of 3-methyl-2-butene-1-aldehyde diisopentenyl acetal
CN112812064A (en) * 2021-01-08 2021-05-18 中国科学院广州生物医药与健康研究院 Organic compound and method for producing the same

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