CN101531578B - Method for preparing axial chirality diaromatic compound with optical activity - Google Patents

Method for preparing axial chirality diaromatic compound with optical activity Download PDF

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CN101531578B
CN101531578B CN200910049510A CN200910049510A CN101531578B CN 101531578 B CN101531578 B CN 101531578B CN 200910049510 A CN200910049510 A CN 200910049510A CN 200910049510 A CN200910049510 A CN 200910049510A CN 101531578 B CN101531578 B CN 101531578B
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compound
chirality
alkyl
diaromatic
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CN101531578A (en
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林国强
徐明华
陈雯雯
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

The invention relates to a method for preparing an axial chirality diaromatic compound with optical activity, which is realized by an asymmetric Ullmann-type coupling reaction catalyzed by chiral monophosphine ligand and nickel composition. The method has the advantages of mild reacting condition, simple and convenient operation and good zymolyte applicability, can prepare the axial chirality diaromatic compound in high stereoselectivity and high yield, and has application prospect of mass synthesis of natural products with axial chirality.

Description

A kind of method for preparing optically active chirality Diaromatic compound
Technical field
The present invention relates to a kind of method for preparing optical activity axle chirality Diaromatic compound.
Background technology
Contain hand and levy the Diaromatic compound of axle; Because it both can be used as chiral ligand and had been widely applied among the asymmetric reaction; Therefore being again many important component parts with the active natural product of important physiological, all is one of emphasis of studying of organic chemist for a long time.The hand of dibenzyl compounds is levied axle and is present in widely in the natural product structure in various dissimilar, different physiologically actives, different biosynthesizing source; Like ((a) Torssell such as tonka bean camphor, flavonoids, tannin, wooden body and vegeto-alkalis; K.G.B.Natural Product Chemistry; Wiley, Chichester 1983; (b) Minitto, P.Biosynthesis of Natural Products, EllisHorwood, Chichester 1981; (c) Thomson, R.H.The Chemistry of Natural Products, 1985; (d) Cordell, G.A.Introduction to Alkaloids, A Biogenetic Appoach, Wiely, NewYork 1981.).
A lot of natural hands that contain are levied the Diaromatic compound of axle physiologically active are all arranged, as: (+)-Talaroderxine A has anti-microbial activity (Suzuki, K.; Nozawa, K.; Nakajima, S.; Udagawa, S.L.; Kawai, K.I.Chem.Pharm.Bull.1992,40,1116.); (-)-Steganone has polymerization (Monovich, the L.G. that stops tubulin; Huerou, Y.L.; Ronn, M.; Molander, G.A.J.Am.Chem.Soc.2000,122,52.); Come to light have HIV-resistant activity (Manfredi, K.P. of Michellamine B; Blunt, J.W.; Cardellina, J.H.; Mcmahon, J.B.; Pannell, L.K.; Gragg, G.M.; Boyd, M.R.J.Med.Chem.1991,34,3402.); And being some aspect that is considered to its anti-microbial activity, Vancomycin surpassed penicillium mould (Penicillin) ((a) .Nagarajan, R.Glycopeptide Antibiotics, MarcelDekker, New York, 1994. (b) .Williams, D.H.; Bardsley, B.Angew.Chem.Int.Ed.1999,38,1173.),
A lot of non-natural hands that contain are levied the Diaromatic compound of axle and are then applied in the various dissimilar asymmetric reactions widely as chiral ligand; Obtained asymmetric induction effect preferably; For example BINAP has been widely applied to ((a) .Ohta, T. in the asymmetric hydrogenation; Takaya, H.; Kitamura, M.; Nagai, K.; Noyori, R.J.Org.Chem.1987,52,3174.; (b) .Takaya, H.; Ohta, T.; Masgima, K.; Noyori, R.Pure&Appl.Chem.1990,62,1135. etc.); BINOL and verivate thereof also are applied in many asymmetric organic reactions at large, have obtained outstanding asymmetric induction effect (Mikami, K.; Matsukawa, S.J.Am.Chem.Soc.1993,115,7039. etc.).
Just because of natural and non-natural contain hand levy the axle Diaromatic compound have particular structure and interesting property, the study on the synthesis of this compounds is one of vitochemical focus always.The structure of levying axle about hand has developed various method so far, is main with methods such as chiral separation and asymmetric synthesis mainly wherein.Through splitting (Kozlowski, M.C.; Dugan, E.C.; DiVirgilio, E.S.; Maksimenka, K.; Bringmann, G.Adv.Synth.Catal.2007,349,583.) obtain hand and levy the method for axle and since development, used till today always, one of the most classical example is exactly to use the verivate of quinine to split BINOL (Wang, Y.; Sun, J.; Ding, K.-L.Tetrahedron 2000,56, and 4447).Result ((a) .Miyano, S. have preferably also been obtained though utilize the asymmetric coupling method of prothetic group inductive; Tobina, M.; Nawa, M.; Sato, S.; Hashimoto, H.J.Chem.Soc.Chem.Commun 1980,24, and 1233; (b). Nelson, T.D.; Meyers, A.I.Tetrahedron Lett.1994,35,3259; (c) .Rawal, V.H.; Florjancic, A.S.; Singh, S.P.Tetrahedron Lett.1994,35,8985; (d) .Lipshutz, B.H.; Siegmann, K.; Garcia, E.J.Am.Chem.Soc.1991,113,8161; (e) .Lipshutz, B.H.; Kayser, F.; Liu, Z.-P.Angew.Chem., Int.Ed.1994,33,1842.), but the asymmetric linked reaction of catalysis has been brought very big convenient ((a) .Hayashi, T.; Hayashizaki, K.; Kiyoi, T.; Ito, Y.J.Am.Chem.Soc.1988,114,8153; (b) .Yin, J.-J.; Buchwald, S.L.J.Am.Chem.Soc.2000,122,12051.).Asymmetric catalysis is a method the most efficient, most economical practicality, yet, problem the such as at present method of development relatively also is not very ripe, can not realize the asymmetric from linked reaction of high steric hindrance substrate, and reaction system is simple and practical inadequately.Therefore exploitation has more Atom economy, and is simple, and practical method will be significant work.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing optically active chirality Diaromatic compound.This method is to utilize chiral monodentate phosphoramidite ligand and the complex-catalyzed asymmetric Ullmann-type linked reaction of nickel (Ni) to realize, utilizes the not chiral ligand of isomorphism type, can obtain the not axle chirality Diaromatic compound of isomorphism type.Related axle chirality Diaromatic compound among the present invention, structure is unique, shows that through preliminary determination of activity the part in them has anti-hepatitis B virus (HBV) effect preferably, might be used to prepare the medicine of diseases such as treatment hepatitis.
Compound method of the present invention can be represented by following type reaction formula:
Figure G2009100495107D00031
Wherein, R 1Be C 1～8Alkoxyl group, C 1～8Alkyl, phenyl, naphthyl, NO 2, COOMe or OR 5
R 2Or/and R 3Be hydrogen, C 1～10Alkyl, C 1～8Alkoxyl group, NO 2, COOMe or OR 5R 2And R 3Can also be-OCH 2O-(epidioxy propyl group), perhaps-CH=CH-CH=CH-;
R 4Be hydrogen, C 1～10Alkyl, C 1～8Alkoxyl group, phenyl, NO 2, COOMe or OR 5
R 5Be H, C 1～10Alkyl, C 1～10The substituted phenyl of acyl group, benzoyl-, benzyl or Z; Z is a hydrogen or halogen.
The chiral monodentate phosphoramidite ligand that utilizes in the method for the present invention has following structural formula:
Figure G2009100495107D00041
Wherein, R 6Be hydrogen, halogen, C 1～8Alkyl, C 1～5Alkoxyl group or benzyloxy;
R 7Be C 1～5Alkyl replaces amine, the substituted amine of phenyl, morphine quinoline, sulfo-morphine quinoline, phenothiazine, C 1～5The substituted piperazine of alkyl, the substituted piperazine of phenyl, the substituted piperazine of pyridine, the substituted piperazine of pyrimidine or the substituted aryl piperazines of Z; Z is a hydrogen, halogen, C 1～5Alkoxyl group or dinaphthalene SULPHOSUCCINIC ACID ESTER.
The structural formula of the typical compound of the chiral monodentate phosphoramidite ligand in this method is following:
Figure G2009100495107D00042
Figure G2009100495107D00051
In the method for the present invention, use molecular formula to be R 1, R 2, R 3Or R 4Substituted adjacent halobenzene benzaldehyde compound is as substrate, and substrate reactions concentration is 0.04～2.0mol/L, and the mol ratio of substrate mole number and divalence or non-valent nickel compound and chiral monophosphorus ligand catalyzer is 100～10: 1; Compare with substrate, add 0.1～1 normal quaternary alkylammonium halides, in polar organic solvent and in the presence of 1.5～4 normal Zn; Under the temperature of room temperature to 80 ℃ (recommending 45 ℃); Reacted 3 to 6 hours, with greater than 60% yield, 55%～67% ee value (is 90～98%ee) to obtain a chirality Diaromatic compound behind the recrystallization.
In the above-mentioned reaction, described divalence or non-valent nickel compound can be two (triphenylphosphine) dihalide nickel (NiX 2(PPh 3) 2) or four (triphenylphosphine) nickel (Ni (PPh 3) 4) etc., wherein X is halogen iodine, bromine or chlorine.
The interpolation of quaternary alkylammonium halides is stabilizing active nickel complex midbody more effectively, promotes the carrying out of reaction.Add 0.5 normal quaternary alkylammonium halides, can add fast response comparatively significantly.Described quaternary alkylammonium halides can be tetrabutylammonium iodide (TBAB), tetraethyl ammonium iodide (TEAB), tetraethylammonium bromide, Tetrabutyl amonium bromide or cetyl trimethylammonium bromide (CTAB).
The solvent that reaction is adopted can be polar solvent N; Dinethylformamide (DMF), DMAC N,N (DMA), glycol dimethyl ether (DME), methyl-sulphoxide (DMSO), HMPA (HMAP), THF (THF) or N-Methyl pyrrolidone (NMP) etc.
Concrete representative experimental results of the present invention is tabulated as follows:
Figure G2009100495107D00061
Method of the present invention is through asymmetric very efficiently Ullmann-type linked reaction of a step; Can be so that selectivity and productive rate prepare a chirality Diaromatic compound preferably; Utilize the characteristic of such product simultaneously, just can obtain the Diaromatic compound of high-optical-purity through a simple recrystallization.React fairly simple, suitability is relatively good, and Atom economy is high.And axle chirality Diaromatic compound related among the present invention shows that through determination of activity the part in them has anti-hepatitis B virus (HBV) effect preferably, might be used to prepare the medicine of diseases such as treatment hepatitis.
The practical implementation method
To help to understand the present invention through following embodiment, but not limit content of the present invention.
Embodiment 1
2a's is synthetic
Feed high-purity argon gas in 10～1000 milliliters of (ml) reaction flasks of exsiccant, add NiCl 2(PPh 3) 2(0.02～20mmol), the chiral monodentate phosphoramidite ligand (0.02～20mmol), and the activatory zinc powder (0.4～400mmol), Bu 4NI (0.1～100mmol), substitute twice in gas after, add the anhydrous DMA of 0.5～500mL; Stirring at room 10min adds the substrate 3,4 that is dissolved in the anhydrous DMA of 0.5～500mL again; 5-trimethoxy 2-bromobenzaldehyde (0.2～200mmol), in argon shield, stirring reaction certain hour under the certain temperature; Be cooled to room temperature then, diatomite filtration is used CH 2Cl 2Wash filter residue three times (3 * 15mL), and the washing organic phase (3 * 20mL), remove DMA as far as possible; Saturated common salt water washing organic phase, anhydrous sodium sulfate drying concentrates; Purification by silica gel column chromatography gets coupled product 2a fast, and productive rate and ee value are referring to table 1 (negative value representes that the product configuration is opposite).
Figure G2009100495107D00071
Table 1
Figure G2009100495107D00072
Figure G2009100495107D00081
Embodiment 2
2a's is synthetic
Feed high-purity argon gas in 10～1000 milliliters of reaction flasks of exsiccant, add NiCl 2(PPh 3) 2(0.02～20mmol), chiral monodentate phosphoramidite ligand (S)-11 (0.02～20mmol), and the activatory zinc powder (0.4～400mmol), Bu 4NI (0.1～100mmol), substitute twice in gas after, add the anhydrous DMA of 0.5～500mL; Stirring at room 10min adds the substrate 3,4 that is dissolved in the anhydrous DMA of 0.5～500mL again; 5-trimethoxy 2-bromobenzaldehyde (0.2～200mmol), in argon shield, stirring reaction certain hour under the certain temperature; Be cooled to room temperature then, diatomite filtration is used CH 2Cl 2Wash filter residue three times (3 * 15mL), and the washing organic phase (3 * 20mL), remove DMA as far as possible, saturated common salt water washing organic phase, anhydrous sodium sulfate drying concentrates, and purification by silica gel column chromatography obtains corresponding coupled product 2a fast, productive rate 67%, the ee value is 67%.
Figure G2009100495107D00082
2a: 1H NMR (300MHz, CDCl 3): δ (ppm) 9.58 (s, 2H, CHO), 7.40 (s, 2H, Ph-H), 4.00 (s, 6H, OCH 3), 3.98 (s, 6H, OCH 3), 3.62 (s, 6H, OCH 3); 13C NMR (300MHz, CDCl 3) δ (ppm) 190.19,153.82,151.53,147.20,130.38,124.34,105.57,61.09,60.69,56.12; ESI-MS (m/z): 391 ([M+H] +), 413 ([M+Na] +); Ultimate analysis: calculated value (EA:calcd for) C 20H 22O 8: C, 61.53; H, 5.68. measured value (Found): C, 61.23; H, 5.65; HPLC: chirality AD-H post (Chiralcel AD-H), hexane/ iPrOH=80: 20, flow velocity (flow rate)=0.7mL/min is measured (detected at) 254nm, t R1=9.7min (minor), t R2=22.6min (major).
Embodiment 3
2b's is synthetic
Operation is with embodiment 2, productive rate 55%, and ee 58%.
Figure G2009100495107D00091
2b： 1H?NMR(300MHz，CDCl 3)δ(ppm)9.56(s，2H，CHO)，7.85(d，J＝8.4Hz，2H，Ph)，7.13(d，J＝8.7Hz，2H，Ph)，4.01(s，6H，OCH 3)，3.61(s，6H，OCH 3)；ESI-MS(m/z)：331([M+H] +)；HPLC：Chiralcel?AD-H，hexane/ iPrOH＝70∶30，flow?rate＝0.7mL/min，detected?at?254nm，t R1＝11.4min(minor)，t R2＝15.5min(major).
Embodiment 4
2c's is synthetic
Operation is with embodiment 3, transformation efficiency 80%, and productive rate 65%, ee 44%.
Figure G2009100495107D00092
2c： 1H?NMR(300MHz，CDCl 3)δ(ppm)9.64(s，2H，CHO)，7.16(d，J＝2.1Hz，2H，Ph)，6.77(d，J＝8.7Hz，2H，Ph)，3.92(s，6H，OCH 3)，3.71(s，6H，OCH 3)； 13C?NMR(300MHz，CDCl 3)δ(ppm)189.88，157.42，146.40，131.23，128.27，125.86，111.86，60.32，55.90；HPLC：Chiralcel?AD-H，hexane/ iPrOH＝70∶30，flowrate＝0.7mL/min，detected?at?254nm，t R1＝11.0min(minor)，t R2＝33.2min(major).
Embodiment 5
2d's is synthetic
Operation is with embodiment 3, productive rate 62%, and ee 61%.
Figure G2009100495107D00101
2d：[α] D 20-1.31(c?0.45，CHCl 3)(for?61％ee)； 1H?NMR(300MHz，CDCl 3)δ(ppm)9.57(s，2H，CHO)，7.81(d，J＝8.4Hz，2H，Ph)，7.35-7.48(m，5H，Ph)，7.19(d，J＝8.4Hz，2H，Ph)，5.25(s，4H，CH 2)，3.64(s，6H，OCH 3)； 13C?NMR(300MHz，CDCl 3)δ(ppm)189.98，156.56，146.84，135.78，131.52，128.71，127.56，128.31，127.38，125.67，113.35，70.76，60.50；ESI-MS(m/z)505([M+Na] +)；FT-IR(KBr)v?2938，1684，1585，1275，1258，1205，1006，739，698cm -1；HRMS?calcd?for?C 30H 26O 6Na +1：505.1627，found：505.1622.HPLC：Chiralcel?AD-H，hexane/ iPrOH＝70∶30，flowrate＝0.7mL/min，detected?at?254nm，t R1＝18.2min(minor)，t R2＝32.8min(major).
Embodiment 6
2e's is synthetic
Operation is with embodiment 3, productive rate 62%, and ee 60%.
Figure G2009100495107D00102
2e：m.p.114-116℃(for?60％ee)；[α] D 20-50.8(c?0.1，CHCl 3)(for?60％ee)； 1H?NMR(300MHz，CDCl 3)δ(ppm)9.51(s，2H，CHO)，7.82(d，J＝8.4Hz，2H，Ph)，6.92-7.19(m，12H，Ph)，7.77(d，J＝1.2Hz，4H，CH 2)，3.98(s，6H，OCH 3)； 13C?NMR(300MHz，CDCl 3)δ(ppm)189.89，157.58，143.55，137.19，131.70，128.63，128.03，127.57，127.42，125.85，111.83，74.21，56.00；ESI-MS(m/z)：483([M+H] +)；FT-IR(KBr)v?2847，1687，1581，1564，1275，1249，1017，749，699cm -1；HRMS?calcd?forC 30H 26O 6Na +1：505.1634，found：505.1622；HPLC：Chiralcel?AD-H，hexane/ iPrOH＝70∶30，flow?rate＝0.7mL/min，detected?at?254nm，t R1＝11.8min(major)，t R2＝12.7min(minor).
Embodiment 7
2f's is synthetic
Operation is with embodiment 3, transformation efficiency 51%, and productive rate 72%, ee 58%.
Figure G2009100495107D00103
2f：m.p.88-90℃(for?rac)；[α] D 20-0.48(c?1.00，CHCl 3)(for?61％ee)； 1H?NMR(300MHz，CDCl 3)：δ(ppm)9.44(s，2H，CHO)，?7.31-7.45(m，12H，Ph)，5.20(s，4H，CH 2)，3.97(s，6H，OCH 3)，3.55(s，6H，OCH 3)；? 13C?NMR(300MHz，CDCl 3)：δ(ppm)190.24，154.10，151.94，145.60，136.58，130.54，128.47，128.31，124.17，105.46，75.00，60.71，56.08；ESI-MS(m/z)：543([M+H] +)；FT-IR(KBr)v?2850，1777，1685，1585，1476，1386，1320，1000，952，697cm -1；ESI-HRMS?calcd?for?C 32H 30O 8Na +1：565.1841，found：565.1833；HPLC：ChiralcelAD-H，hexane/ iPrOH＝70∶30，flow?rate＝0.7mL/min，detected?at?254nm，t R1＝9.3min(minor)，t R2＝13.2min(major).
Embodiment 8
The recrystallization operation
100mg～10g 67%ee compound 2a is dissolved in about 6～600mL absolute ethyl alcohol under the heating, and this clear liquid is left standstill; Make it naturally cool to room temperature; Be positioned over refrigerator-20 ℃ environment then following 2 hours, and filtered out the white solid of being separated out, white solid is measured as the 3%ee value; Mother liquor concentrates, and is measured as the 98%ee value, and the recrystallization yield is 60%.

Claims (6)

1. one kind prepares a method of chirality Diaromatic compound; It is characterized in that under the temperature of room temperature to 80 ℃; In the presence of zinc powder, quaternary alkylammonium halides and organic polar solvent, the adjacent halobenzene benzaldehyde compound reaction of chiral monophosphorus ligand and nickel complex as catalyst agent catalytic substrate 3～6 hours;
Wherein, concentration of substrate is 0.04～2.0 mole/L, and substrate mole number and catalyzer mole ratio are 100～5: 1, compares with substrate, adopts 1.5～4 equivalent zinc powders and 0.1～1 normal quaternary alkylammonium halides;
Described nickel complex as catalyst agent is two (triphenylphosphine) Nickel Chloride, two (triphenylphosphine) Nickel Bromides or two (triphenylphosphines), two nickelous iodides or four (triphenylphosphine) nickel;
Described reaction has following reaction formula:
Figure FSB00000780985600011
Wherein, R 1Be C 1～8Alkoxyl group or C 1～8Alkyl;
R 2Or/and R 3Be hydrogen, C 1～10Alkyl, C 1～8Alkoxyl group or COOMe;
R 4Be hydrogen, C 1～10Alkyl or C 1～8Alkoxyl group.
2. a kind of method of chirality Diaromatic compound for preparing as claimed in claim 1 is characterized in that described chiral monophosphorus ligand has following structural formula:
Figure FSB00000780985600012
Wherein, R 6Be hydrogen, halogen, C 1～8Alkyl, C 1～5Alkoxyl group or benzyloxy;
R 7Be C 1～5Alkyl replaces amine, the substituted amine of aryl, C 1～5The substituted piperazine of alkyl, the substituted piperazine of aryl, morphine quinoline, C 1～5Substituted piperazine of alkyl or sulfo-morphine quinoline.
3. the compound method of a kind of chirality Diaromatic compound as claimed in claim 1 is characterized in that described chiral monophosphorus ligand (monodentate phosphoramidite ligand) has following structural formula:
Figure FSB00000780985600021
4. the compound method of a kind of chirality Diaromatic compound as claimed in claim 3 is characterized in that described additive quaternary alkylammonium halides is tetrabutylammonium iodide, tetraethyl ammonium iodide, tetraethylammonium bromide, Tetrabutyl amonium bromide or cetyl trimethylammonium bromide.
5. the compound method of a kind of chirality Diaromatic compound as claimed in claim 3; It is characterized in that described polar organic solvent is N; Dinethylformamide, DMAC N,N, glycol dimethyl ether, methyl-sulphoxide, HMPA, THF or N-Methyl pyrrolidone.
6. the compound method of a kind of chirality Diaromatic compound as claimed in claim 3 is characterized in that described temperature of reaction is 45 ℃.
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