CN104119382A - 1,3-disubstituted-allylphosphine oxide compounds and preparation method thereof - Google Patents

1,3-disubstituted-allylphosphine oxide compounds and preparation method thereof Download PDF

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CN104119382A
CN104119382A CN201410336381.0A CN201410336381A CN104119382A CN 104119382 A CN104119382 A CN 104119382A CN 201410336381 A CN201410336381 A CN 201410336381A CN 104119382 A CN104119382 A CN 104119382A
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oxygen
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phosphorus compound
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赵晓明
张亮
刘炜
张红波
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Tongji University
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Tongji University
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Abstract

The invention relates to 1,3-disubstituted-allylphosphine oxide compounds and a preparation method thereof. The preparation method comprises the following steps: adding raw materials namely diphenylphosphine oxide and allyl methyl carbonate into an organic solvent, controlling the reaction temperature in a range of 25 to 60 DEG C, and making the raw materials carry out reactions for 1 to 12 hours in the presence of a palladium complex catalyst, which is prepared by carrying out reactions between Pd2(dba)3 and a ligand, so as to obtain the 1,3-disubstituted-allylphosphine oxide compound. Compared to the prior art, the preparation method has the advantages of available catalyst, high catalyst activity, mild reaction conditions, and wide substrate application range.

Description

Phosphorus compound of a kind of 1,3-, bis-substituted allyl oxygen and preparation method thereof
Technical field
The invention belongs to chemosynthesis technical field, relate to Phosphorus compound of a kind of 1,3-, bis-substituted allyl oxygen and preparation method thereof.
Background technology
Organic phosphine compound can be widely used in all respects such as organic synthesis, medicine, agricultural chemicals, part be synthetic.Pertinent literature report has: (a) Johansson, T.; Stawinski, J.Nucleosides, Nucleotides Nucleic Acids2003,22,1459; (b) Bialy, L.; Waldmann, H.Angew.Chem., Int.Ed.2005,44,3814; (c) George, A.; Veis, A.Chem.Rev.2008,108,4670; (d) Albrecht, L.; Albrecht, A.; Krawczyk, H.; Jorgensen, K.A.Chem.; Eur.J.2010,16,28; (e) Jeught, S.V.; Stevens, C.V.Chem.Rev.2009,109,2672; (f) Alexandre, F.; Amador, A.; Bot, S.; Caillet, C.; Convard, T.; Jakubik, J.; Musiu, C.; Poddesu, B.; Vargiu, L.; Liuzzi, M.; Roland, A.; Seifer, M.; Standring, D.; Storer, R.; Dousson, C.B.J.Med.Chem.2011,54,392; (g) Zhao, D.; Wang, R.Chem.Soc.Rev.2012,41,2095.
At present, the phosphorus compound with chirality is to be widely used in laboratory and the industrial potential part of asymmetry catalysis that does, but the research aspect synthesizing chiral phosphine compounds method is very few.Pertinent literature report has: (a) Glueck, D.S.Synlett2007,2627; (b) Glueck, D.S.Chem.-Eur.J.2008,14,7108; (c) Harvey, J.S.; Gouverneur, V.Chem.Commun.2010,7477; (c) Kovacik, I.; Wicht, D.K.; Grewal, N.S.; Glueck, D.S.; Incarvito, C.D.; Guzei, I.A.; Rheingold, A.L.Organometallics2000,19,950; (d) Moncarz, J.R.; Laritcheva, N.F.; Glueck, D.S., J.Am.Chem.Soc.2002,124,13356; (e) Sadow, A.D.; Haller, I.; Fadini, L.; Togni, A.J.Am.Chem.Soc.2004,126,14704; (f) Scriban, C.; Kovacik, I.; Glueck, D.S.Organometallics2005,24,4871; (g) Chan, V.S.; Stewart, I.C.; Bergman, R.G.; Toste, F.D.J.Am.Chem.Soc.2006,128,2786; (h) Butti, P.; Rochat, R.; Sadow, A.D.; Togni, A.Angew.Chem., Int.Ed.2008,47,4878.Up to the present, synthesize by allylation reaction the relevant report that contains optically active organic phosphine compound also considerably less.And in part application, chiral phosphorus ligand in occupation of and consequence, thereby synthesis of chiral phosphorus compound is necessary and significant.
Summary of the invention
Object of the present invention is exactly to provide Phosphorus compound of a kind of 1,3-, bis-substituted allyl oxygen and preparation method thereof in order to overcome the defect that above-mentioned prior art exists.
Object of the present invention can be achieved through the following technical solutions:
The Phosphorus compound of a kind of 1,3-, bis-substituted allyl oxygen, the structural formula of this compound is: wherein * is chiral carbon atom, and R is phenyl ring or contains substituent aryl.
The preparation method of the Phosphorus compound of a kind of 1,3-, bis-substituted allyl oxygen, the method is using chirality palladium complex as catalyzer, carries out high enantioselective reactions by allyl carbonate methyl esters, diphenyl phosphate oxygen, specifically comprises the following steps:
(1) diphenyl phosphate oxygen and allyl carbonate methyl esters are joined in organic solvent, fully stir, then add catalyzer, controlling temperature of reaction is 25 DEG C～60 DEG C, and reaction 1～12h, makes crude product;
(2) crude product step (1) being made carries out separating-purifying, i.e. the synthetic Phosphorus compound of 1,3-, bis-substituted allyl oxygen that obtains.
The described catalyzer of step (1) is with Pd 2(dba) 3palladium complex with part effect generation.
Described allyl carbonate methyl esters, diphenyl phosphate oxygen, Pd 2(dba) 3and the mol ratio of part is (1.2～5): 1: 0.05: 0.1; Preferably, allyl carbonate methyl esters, diphenyl phosphate oxygen, Pd 2(dba) 3and the mol ratio of part is 5: 1: 0.05: 0.1.
Preferably 55 DEG C of temperature of reaction described in step (1).
The described organic solvent of step (1) is one or more in toluene, methylene dichloride, tetrahydrofuran (THF).
The structural formula of described diphenyl phosphate oxygen is the structural formula of described allyl carbonate methyl esters is wherein R is phenyl ring or contains substituent aryl, and described part is optical purity part,
Its structural formula is in one.
The method of the described separating-purifying of step (2) is one or more in thin-layer chromatography, column chromatography and underpressure distillation.Described thin-layer chromatography, column chromatography, developping agent used is the mixed solvent of non-polar solvent and polar solvent, preferably sherwood oil-methylene dichloride, petroleum ether-ethyl acetate, the mixed solvents such as sherwood oil-ether, preferably, the volume of non-polar solvent and polar solvent is 1: 1.
Compared with prior art, the present invention has following characteristics:
1. preparation process of the present invention is simple, and reaction conditions gentleness is applicable to dissimilar allyl carbonate methyl esters compounds;
2. used catalyst of the present invention is easy to get, and catalytic activity is high, wide application range of substrates, and reaction yield is high, can reach 95%, and enantioselectivity is high, is 65%～96%.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
The research of allyl carbonate methyl esters, diphenyloxide phosphorus ratio, temperature and the solvent of palladium complex catalysis, and the impact on reaction of different palladiums source, part, wherein L assignment body, solvent refers to solvent, T refers to temperature.
Wherein, DCM is methylene dichloride, and Toluene is toluene, and THF is tetrahydrofuran (THF).The different part using in reaction:
Embodiment 2
Allyl carbonate methyl esters, the diphenyl phosphate oxygen allylation reaction of palladium complex catalysis are:
In the reaction tubes of a dry argon shield, add successively Pd 2(dba) 3(0.05mmol), chiral ligand (0.01mmol) toluene (2.0mL) reacts 30 minutes at 25 DEG C.In reaction tubes, add allyl carbonate methyl esters (0.5mmol), 55 DEG C of stirring reactions of diphenyl phosphate oxygen (0.1mmol).After reaction finishes, after removal of solvent under reduced pressure, residue thin-layer chromatography obtains target product 3 (petrol ether/ethyl acetate=1: 1, v/v).
P1:(E)-1,3-bis-(4-fluorophenyl)-allyl carbonate methyl esters
Colourless liquid, 85% yield.
1H?NMR(400MHz，CDCl3)δ＝7.41(dd，J＝8.6，5.4Hz，2H)，7.32(dd，J＝8.6，5.5Hz，2H)，7.06(t，J＝8.6Hz，2H)，6.98(t，J＝8.6Hz，2H)，6.70-6.57(m，1H)，6.27(dd，J＝13.1，5.0Hz，2H)，3.78(s，3H). 13C?NMR(100MHz，CDCl3)δ＝163.9，161.5(d，J＝1.0Hz)，155.0，134.6(d，J＝3.2Hz)，132.2(d，J＝3.3Hz)，131.9，129.0(d，J＝8.3Hz)，128.4(d，J＝8.3Hz)，126.5(d，J＝1.8Hz)，115.7(d，J＝6.9Hz)，115.5(d，J＝7.0Hz)，79.4，54.8. 19F?NMR(377MHz，CDCl3)δ＝-113.11(d，J＝8.6Hz).IR(KBr)：v max(cm -1)＝3038，2961，2851，1744，1607，1506，1444，1298，1265，1155，1092，970，836，789，503，468.HRMS(EI)calcd?for?C 17H 14F 2NaO 3[M+Na] +：327.0803，Found：327.0803.
P2:(E)-1,3-bis-(4-chloro-phenyl-)-allyl carbonate methyl esters
White solid, fusing point: 95.5-97.1 DEG C, 81% yield.
1H?NMR(400MHz，CDCl3)δ＝7.35(s，4H)，7.28(d，J＝2.3Hz，4H)，6.61(d，J＝15.6Hz，1H)，6.28(dd，J＝15.7，6.7Hz，1H)，6.21(d，J＝6.8Hz，1H)，3.79(s，3H). 13C?NMR(100MHz，CDCl3)δ＝155.0，137.0，134.4，134.3，134.1，132.1，129.0，128.8，128.4，128.0，127.0，79.2，55.0.IR(KBr)：v max(cm -1)＝3029，2955，2848，1747，1586，1491，1434，1259，1086，1018，958，827，786，562，488，449.HRMS(EI)calcd?for?C 17H 14Cl 2NaO 3[M+Na] +：359.0212，Found：359.0211.
P3:(E)-1,3-bis-(4-bromophenyl)-allyl carbonate methyl esters
White solid, fusing point: 88.0-89.7 DEG C, 83% yield.
1H?NMR(400MHz，CDCl3)δ＝7.49(d，J＝8.3Hz，2H)，7.41(d，J＝8.4Hz，2H)，7.23(t，J＝9.0Hz，4H)，6.54(d，J＝15.9Hz，1H)，6.20(dd，J＝15.9，6.8Hz，1H)，4.74(d，J＝6.8Hz，1H)，3.35(s，3H). 13C?NMR(100MHz，CDCl3)δ＝139.8，135.3，131.7，130.6，130.5，128.6，128.1，121.7，83.5，56.6.IR(KBr)：v max(cm -1)＝3021，2922，2815，1637，1550，1485，1396，1190，1071，1009，964，818，500.HRMS(EI)calcd?for?C 17H 14Br 2NaO 3[M+Na] +：449.9202，Found：449.9202.
P4:(E)-1,3-bis-(3-fluorophenyl)-allyl carbonate methyl esters
White solid, fusing point: 60.5-61.5 DEG C, 80% yield.
1H?NMR(400MHz，CDCl3)δ＝7.39-7.31(m，1H)，7.30-7.23(m，1H)，7.19(d，J＝7.7Hz，1H)，7.14(d，J＝7.8Hz，2H)，7.04(ddd，J＝12.2，10.5，6.2Hz，2H)，6.95(td，J＝8.3，2.0Hz，1H)，6.66(d，J＝15.7Hz，1H)，6.32(dd，J＝15.7，6.8Hz，1H)，6.23(d，J＝6.8Hz，1H)，3.81(s，3H). 13C?NMR(100MHz，CDCl3)δ＝164.2(d，J＝10.1Hz)，161.8(d，J＝11.2Hz)，154.9，140.8(d，J＝7.1Hz)，138.1(d，J＝7.6Hz)，132.2(d，J＝2.5Hz)，130.4(d，J＝8.2Hz)，130.1(d，J＝8.4Hz)，127.6，122.8(d，J＝2.8Hz)，122.5(d，J＝3.0Hz)，115.5(d，J＝21.1Hz)，115.2(d，J＝21.4Hz)，113.9(d，J＝22.5Hz)，113.4(d，J＝21.9Hz)，79.1(d，J＝1.7Hz)，55.04. 19F?NMR(377MHz，CDCl3)δ＝-112.07(s)，-113.19(s).IR(KBr)：v max(cm -1)＝3062，3035，2958，2848，1747，1613，1589，1485，1443，1256，1140，958，872，783，678，524，494，452.HRMS(EI)calcd?for?C 17H 14F 2NaO 3[M+Na] +：327.0803，Found：327.0805.
P5:(E)-1,3-bis-(3-chloro-phenyl-)-allyl carbonate methyl esters
White solid, fusing point: 74.9-76.5 DEG C,, 79% yield.
1H?NMR(400MHz，CDCl3)δ＝7.41(s，1H)，7.36(s，1H)，7.34-7.25(m，3H)，7.26-7.18(m，3H)，6.63(d，J＝15.8Hz，1H)，6.31(dd，J＝15.7，6.8Hz，1H)，6.20(d，J＝6.8Hz，1H)，3.80(s，3H). 13C?NMR(100MHz，CDCl3)δ＝154.9，140.4，137.6，134.7，134.6，132.0，130.1，129.9，128.7，128.3，126.7，125.1，125.0，79.0，55.1.IR(KBr)：v max(cm -1)＝3050，2916，2363，1785，1765，1723，1657，1580，1482，1440，1387，1018，750，684，580，559.HRMS(EI)calcd?for?C 17H 14Cl 2NaO 3[M+Na] +：359.0212，Found：359.0210.
P6:(E)-1,3-bis-(4-aminomethyl phenyl)-allyl carbonate methyl esters
Colourless liquid, 65% yield.
1H?NMR(400MHz，CDCl3)δ＝7.31(d，J＝8.0Hz，2H)，7.24(s，2H)，7.16(d，J＝7.9Hz，2H)，7.08(d，J＝7.9Hz，2H)，6.63(d，J＝15.7Hz，1H)，6.31(dd，J＝15.7，6.9Hz，1H)，6.24-6.18(m，1H)，3.75(s，3H)，2.31(d，J＝11.3Hz，6H). 13C?NMR(100MHz，CDCl3)δ＝155.2，138.3，138.1，135.9，133.4，132.9，129.4，129.3，127.1，126.7，126.0，80.4，54.8，21.3，21.2.IR(KBr)：v max(cm -1)＝3021，2958，2919，1645，1509，1440，1259，1178，1089，961，797，580，512.HRMS(EI)calcd?for?C 19H 22NaO 3[M+Na] +：321.1461，Found：321.1454.
P7:(E)-1,3-bis-(3-aminomethyl phenyl)-allyl carbonate methyl esters
White solid, fusing point: 79.5-80.5 DEG C, 60% yield.
1H?NMR(400MHz，CDCl3)δ＝7.23(d，J＝5.8Hz，3H)，7.18-7.13(m，3H)，7.09(d，J＝5.1Hz，1H)，7.04-6.96(m，1H)，6.65(d，J＝15.7Hz，1H)，6.34(dd，J＝15.7，6.9Hz，1H)，6.22(d，J＝6.9Hz，1H)，3.73(s，3H)，2.30(d，J＝18.1Hz，6H). 13C?NMR(100MHz，CDCl3)δ＝155.2，138.8，138.5，138.2，136.2，133.1，129.3，129.1，128.7，128.6，127.7，127.6，126.9，124.2，124.1，80.5，54.8，21.5，21.4.IR(KBr)：v max(cm -1)＝3023，2936，1658，1511，1451，1248，1178，1101，962，797，581，512.HRMS(EI)calcd?for?C 19H 22NaO 3[M+Na] +：321.1461，Found：321.1454.
P8:(E)-1,3-bis-(1-naphthyl) allyl carbonate methyl esters
Yellow liquid, 71% yield.
1H?NMR(400MHz，CDCl3)δ＝8.30(d，J＝8.5Hz，1H)，7.94(d，J＝7.5Hz，1H)，7.76(dd，J＝18.1，7.8Hz，4H)，7.72-7.65(m，2H)，7.62(d，J＝8.1Hz，2H)，7.55-7.46(m，3H)，7.42(t，J＝7.4Hz，3H)，7.38-7.32(m，3H)，7.23(t，J＝7.7Hz，1H)，7.11(d，J＝6.1Hz，1H)，6.56(dd，J＝15.6，6.2Hz，1H)，3.72(s，3H). 13C?NMR(100MHz，CDCl3)δ＝155.5，134.4，134.2，134.0，133.7，131.4，131.0，130.8，130.0，129.5，129.1，128.7，126.7，126.4，126.1，126.0，125.7，125.6，124.3，124.0，123.8，78.3，55.1，46.5，11.8.IR(KBr)：v max(cm -1)＝3047，2952，2851，1750，1595，1515，1440，1268，937，777.HRMS(EI)calcd?for?C 25H 20NaO 3[M+Na] +：391.1305，Found：391.1305.
P9:(E)-1,3-bis-(2-naphthyl) allyl carbonate methyl esters
Yellow liquid,, 75% yield.
1H?NMR(400MHz，CDCl3)δ＝7.90-7.81(m，1H)，7.79-7.72(m，1H)，7.59(d，J＝8.6Hz，1H)，7.54(d，J＝8.5Hz，1H)，7.51-7.45(m，1H)，7.46-7.39(m，1H)，6.83(d，J＝15.9Hz，1H)，6.49(dd，J＝15.9，6.8Hz，1H)，5.03(d，J＝6.7Hz，1H)，3.44(s，1H). 13C?NMR(101MHz，CDCl3)δ＝138.4，134.1，133.6，133.4，133.2，133.1，131.7，130.6，128.5，128.2，128.0，127.8，127.7，126.7，126.3，126.2，126.0，125.9，125.8，124.9，123.7，84.5，56.6，46.3，11.4.IR(KBr)：v max(cm -1)＝3056，2928，2818，1747，1598，1500，1268，1095，967，854，815，747，470.HRMS(EI)calcd?for?C25H20NaO3[M+Na] +：391.1305，Found：391.1305.
P10:(E)-(1,3-phenylbenzene allyl group)-diphenyl phosphate oxygen
White solid, fusing point: 243.5-245.5 DEG C, 95% yield, 96%ee.[chiral column IC-H (0.46cm x25cm); Normal hexane/Virahol=70/30; Flow velocity=1.0mL/min; Detect wavelength=254nm; t r=10.735 (minor), 14.486 (major) min].
[α] D 20＝+10.1°(c0.5，CHCl 3).
1H?NMR(400MHz，CDCl 3)δ7.62-7.54(m，1H)，7.52-7.43(m，1H)，7.41-7.27(m，3H)，7.19(dt，J＝14.3，6.3Hz，4H)，6.58(ddd，J＝16.0，9.0，7.3Hz，1H)，6.32(dd，J＝15.8，3.7Hz，1H)，4.36(t，J＝9.4Hz，1H). 13C?NMR(101MHz，CDCl3)δ＝136.7(d，J＝2.3Hz)，135.9(d，J＝2.3Hz)，134.4(d，J＝11.2Hz)，132.0(d，J＝67.5Hz)，131.8，131.7(d，J＝67.4Hz)，131.5(d，J＝2.7Hz)，131.3，131.1，129.5(d，J＝5.8Hz)，128.6(d，J＝1.6Hz)，128.5(d，J＝11.4Hz)，128.4，128.2(d，J＝11.5Hz)，127.6，127.1(d，J＝2.3Hz)，126.4(d，J＝1.3Hz)，124.6(d，J＝7.2Hz)，52.4(d，J＝64.7Hz). 31P?NMR(162MHz，CDCl3)δ＝31.42(s).IR(KBr)：v max(cm -1)＝3059，2920，2845，1489，1438，1170，1117，962，748，727，694，545，498.HRMS(EI)calcd?for?C 27H 23NaOP[M+Na] +：417.1379，Found：417.1384.
P11:(E)-(1,3-bis-(4-fluorophenyl)-allyl group)-diphenyl phosphate oxygen
White solid, fusing point: 213.6-215.3 DEG C, 75% yield .94%ee.[chiral column IC-H (0.46cm x25cm); Normal hexane/Virahol=70/30; Flow velocity=1.0mL/min; Detect wavelength=254nm; t r=7.376 (minor), 8.327 (major) min].
[α] D 20＝-12.4°(c0.5，CHCl 3).
1H?NMR(400MHz，CDCl 3)δ7.93-7.78(m，1H)，7.64-7.53(m，1H)，7.53-7.44(m，1H)，7.41(dd，J＝10.5，4.2Hz，1H)，7.37-7.27(m，2H)，7.16(dd，J＝8.5，5.5Hz，1H)，6.92(t，J＝8.6Hz，2H)，6.44(ddd，J＝15.9，8.7，7.3Hz，1H)，6.26(dd，J＝15.8，3.5Hz，1H)，4.34(t，J＝9.2Hz，1H). 13C?NMR(101MHz，CDCl3)δ＝163.6(d，J＝38.7Hz)，161.6(d，J＝37.7Hz)，137.9(d，J＝2.6Hz)133.4(d，J＝11.0Hz)，131.2，131.0，130.9(d，J＝2.1Hz)，130.8，128.5(d，J＝11.4Hz)，128.3(d，J＝11.6Hz)，127.9，127.8，124.1(d，J＝5.2Hz)，115.6，115.4，115.3(d，J＝21.5Hz)，51.6(d，J＝65.0Hz). 19F?NMR(377MHz，CDCl3)δ＝-114.09(s)，-115.10(d，J＝3.6Hz). 31P?NMR(162MHz，CDCl3)δ＝31.33(s).IR(KBr)：v max(cm -1)＝3056，2919，2848，1601，1506，1440，1372，1226，1178，1158，1116，967，836，7000，566，542.HRMS(EI)calcd?for?C 27H 21F 2NaOP[M+Na] +：453.1190，Found：453.1188.
P12:(E)-(1,3-bis-(4-chloro-phenyl-)-allyl group)-diphenyl phosphate oxygen
White solid, fusing point: 236.9-238.3 DEG C, 92% yield .90%ee.[chiral column IC-H (0.46cm x25cm); Normal hexane/Virahol=70/30; Flow velocity=1.0mL/min; Detect wavelength=254nm; t r=31.437 (minor), 35.267 (major) min].
[α] D 20＝-5.2°(c0.5，CHCl 3).
1H?NMR(400MHz，CDCl 3)δ7.89-7.78(m，1H)，7.63-7.55(m，1H)，7.54-7.46(m，1H)，7.42(d，J＝7.4Hz，1H)，7.37-7.27(m，2H)，7.20(d，J＝8.5Hz，2H)，7.11(d，J＝8.4Hz，1H)，6.48(ddd，J＝15.9，8.9，7.2Hz，1H)，6.23(dd，J＝15.8，3.6Hz，1H)，4.32(t，J＝9.2Hz，1H). 13C?NMR(101MHz，CDCl3)δ＝135.0(d，J＝2.6Hz)，134.3(d，J＝5.9Hz)，133.5(d，J＝2.3Hz)133.4，133.2(d，J＝3.3Hz)，132.0，131.8(d，J＝7.7Hz)，131.7(d，J＝59.5Hz)，131.6(d，J＝8.5Hz)，131.5(d，J＝54.3Hz)，130.9，130.7(d，J＝5.8Hz)，128.8(d，J＝1.5Hz)，128.7，128.6(d，J＝11.5Hz)，128.4(d，J＝11.6Hz)，127.6(d，J＝1.0Hz)，124.8(d，J＝7.1Hz)，51.5(d，J＝64.4Hz). 31P?NMR(162MHz，CDCl3)δ＝31.11(s).IR(KBr)：v max(cm -1)＝3053，2928，2848，1539，1485，1399，1092，967，860，723，548，524.HRMS(EI)calcd?for?C 27H 21Cl 2NaOP[M+Na] +：485.0599，Found：485.0597.
P13:(E)-(1,3-bis-(4-bromophenyl)-allyl group)-diphenyl phosphate oxygen
White solid, fusing point: 222.4-223.3 DEG C, 62% yield .94%ee.[chiral column IC-H (0.46cm x25cm); Normal hexane/Virahol=90/10; Flow velocity=0.8mL/min; Detect wavelength=254nm; t r=45.916 (minor), 48.749 (major) min].
[α] D 20＝-12.3°(c0.5，CHCl 3).
1H?NMR(400MHz，CDCl 3)δ7.91-7.75(m，2H)，7.63-7.55(m，2H)，7.54-7.43(m，3H)，7.41(d，J＝7.3Hz，1H)，7.38-7.30(m，6H)，7.26-7.20(m，2H)，7.04(d，J＝8.4Hz，2H)，6.49(ddd，J＝16.0，8.9，7.2Hz，1H)，6.21(dd，J＝15.8，3.6Hz，1H)，4.32(t，J＝9.2Hz，1H). 13C?NMR(101MHz，CDCl3)δ＝135.4(d，J＝2.2Hz)，134.8(d，J＝5.8Hz)，133.6(d，J＝11.0Hz)132.0(d，J＝2.6Hz)，131.8(d，J＝2.7Hz)，131.6，131.5(d，J＝2.7Hz)，131.2(d，J＝17.5Hz)，131.1(d，J＝14.4Hz)，130.8(d，J＝13.1Hz)，128.5(d，J＝16.6Hz)，127.8，124.9(d，J＝7.1Hz)，121.6，121.4(d，J＝2.9Hz)，51.7(d，J＝64.2Hz). 31P?NMR(162MHz，CDCl3)δ＝30.96(s).IR(KBr)：v max(cm -1)＝3050，2922，2848，1586，1485，1435，1369，1184，1116，1069，1012，959，720，572，542，515.HRMS(EI)calcd?for?C 27H 21Br 2NaOP[M+Na] +：572.9589，Found：572.9585.
P14:(E)-(1,3-bis-(3-fluorophenyl)-allyl group)-diphenyl phosphate oxygen
White solid, fusing point: 206.4-207.3 DEG C, 93% yield .86%ee.[chiral column IC-H (0.46cm x25cm); Normal hexane/Virahol=70/30; Flow velocity=1.0mL/min; Detect wavelength=254nm; t r=7.375 (minor), 8.269 (major) min].
[α] D 20＝-16.2°(c0.5，CHCl 3).
1H?NMR(400MHz，CDCl 3)δ7.92-7.75(m，1H)，7.66-7.56(m，1H)，7.56-7.45(m，1H)，7.41(td，J＝7.4，1.2Hz，1H)，7.37-7.30(m，1H)，7.23-7.13(m，2H)，7.10(d，J＝9.8Hz，1H)，6.97(d，J＝7.7Hz，1H)，6.88(dd，J＝13.7，5.4Hz，1H)，6.54(ddd，J＝16.0，9.0，7.1Hz，1H)，6.27(dd，J＝15.9，3.6Hz，1H)，4.36(t，J＝9.3Hz，1H). 13C?NMR(101MHz，CDCl3)δ＝164.1(d，J＝26.5Hz)，161.7(d，J＝27.2Hz)，138.8(d，J＝2.4Hz)，138.7(d，J＝2.4Hz)，138.2(d，J＝5.9Hz)，138.0(d，J＝7.6Hz)，133.6(d，J＝2.5Hz)，133.5(d，J＝2.5Hz)，132.0(d，J＝2.7Hz)，131.8(d，J＝2.7Hz)，131.4(d，J＝37.0Hz)131.2，131.0，130.9(d，J＝2.1Hz)，130.8，128.5(d，J＝11.4Hz)，128.3(d，J＝11.6Hz)，127.9，127.8，124.1(d，J＝5.2Hz)，115.6，115.4，115.3(d，J＝21.5Hz)，51.6(d，J＝65.0Hz). 19F?NMR(376MHz，CDCl3)δ＝-112.33(s)，-113.45(s). 31P?NMR(162MHz，CDCl3)δ＝31.06(s).IR(KBr)：v max(cm -1)＝3056，2917，2848，1610，1586，1482，1434，1250，1185，1116，965，774，718，697，589，560，548.HRMS(EI)calcd?for?C 27H 21F 2NaOP[M+Na] +：453.1190，Found：453.1185.
P15:(E)-(1,3-bis-(3-chloro-phenyl-)-allyl group)-diphenyl phosphate oxygen
White solid, fusing point: 173.5-2175.3 DEG C, 72% yield .95%ee.[chiral column IC-H (0.46cm x25cm); Normal hexane/Virahol=70/30; Flow velocity=1.0mL/min; Detect wavelength=254nm; t r=28.156 (minor), 29.976 (major) min].
[α] D 20＝-5.6°(c0.5，CHCl 3).
1H?NMR(400MHz，CDCl3)δ7.93-7.80(m，1H)，7.65-7.56(m，1H)，7.55-7.45(m，2H)，7.42(t，J＝6.9Hz，1H)，7.38-7.27(m，2H)，7.16(dd，J＝8.7，4.8Hz，2H)，7.07(d，J＝3.5Hz，1H)，6.54(ddd，J＝16.1，9.1，7.2Hz，1H)，6.24(dd，J＝15.8，3.6Hz，1H)，4.33(t，J＝9.3Hz，1H). 13C?NMR(101MHz，CDCl3)δ＝138.3(d，J＝2.4Hz)，137.8(d，J＝5.9Hz)，135.4，134.5，134.3(d，J＝1.6Hz)，133.5(d，J＝11.0Hz)，132.1(d，J＝2.6Hz)，131.9(d，J＝2.7Hz)，131.6(d，J＝8.4Hz)，131.0(d，J＝66.3Hz)，130.9(d，J＝58.1Hz)，129.8(d，J＝1.6Hz)，129.5(d，J＝6.0Hz)129.1，128.6(d，J＝11.5Hz)，128.4(d，J＝11.6Hz)，127.7，127.6(d，J＝5.5Hz)，127.5(d，J＝2.1Hz)，126.4，125.6(d，J＝7.2Hz)，124.5(d，J＝1.0Hz)，52.0(d，J＝63.9Hz). 31PNMR(162MHz，CDCl3)δ＝31.11(s).IR(KBr)：v max(cm -1)＝3057，2923，2849，1590，1566，1477，1435，1179，1111，962，781，721，697，578，563，516.
HRMS(EI)calcd?for?C 27H 21Cl 2NaOP[M+Na] +：485.0599，Found：485.0597.
P16:(E)-(1,3-bis-(4-aminomethyl phenyl)-allyl group)-diphenyl phosphate oxygen
White solid, fusing point: 223.6-225.4 DEG C, 45% yield .70%ee[chiral column IC-H (0.46cm x25cm); Normal hexane/Virahol=70/30; Flow velocity=1.0mL/min; Detect wavelength=254nm; t r=12.800 (minor), 13.958 (major) min].
[α] D 20＝-12.1°(c0.5，CHCl 3).
1H?NMR(400MHz，CDCl3)δ7.83(dd，J＝9.6，8.0Hz，1H)，7.65-7.56(m，1H)，7.53-7.41(m，2H)，7.39(d，J＝7.0Hz，1H)，7.32(td，J＝7.5，2.7Hz，1H)，7.22(d，J＝6.7Hz，1H)，7.10(d，J＝8.0Hz，1H)，7.03(d，J＝7.9Hz，2H)，6.50(ddd，J＝16.0，8.9，7.2Hz，1H)，6.25(dd，J＝15.8，3.7Hz，1H)，4.33(t，J＝9.6Hz，1H)，2.27(d，J＝7.6Hz，3H). 13C?NMR(101MHz，CDCl3)δ＝137.4，136.7(d，J＝2.2Hz)，134.1，134.0，132.9(d，J＝6.0Hz)，132.2(d，J＝75.0Hz)，132.0(d，J＝53.0Hz)，131.6(d，J＝2.7Hz)，131.5，131.4，129.3，129.2，129.1，128.4(d，J＝11.4Hz)，128.2(d，J＝11.4Hz)，126.3(d，J＝1.2Hz)，123.7(d，J＝7.1Hz)，52.2(d，J＝65.2Hz)，21.1(d，J＝9.8Hz). 31P?NMR(162MHz，CDCl3)δ＝31.40(s).IR(KBr)：v max(cm -1)＝3053，2919，1857，1512，1434，1378，1176，1113，965，795，699，566，539，506.HRMS(EI)calcd?for?C 29H 27NaOP[M+Na] +：445.1692，Found：445.1694.
P17:(E)-(1,3-bis-(3-aminomethyl phenyl)-allyl group)-diphenyl phosphate oxygen
White solid, fusing point: 168.6-170.1 DEG C, 53% yield .88%ee[chiral column IC-H (0.46cm x25cm); Normal hexane/Virahol=70/30; Flow velocity=1.0mL/min; Detect wavelength=254nm; t r=11.438 (minor), 13.702 (major) min].
[α] D 20＝-4.0°(c0.5，CHCl 3).
1H?NMR(400MHz，CDCl 3)δ7.91-7.77(m，1H)，7.64-7.53(m，1H)，7.53-7.42(m，1H)，7.38(t，J＝6.8Hz，1H)，7.30(td，J＝7.6，2.7Hz，1H)，7.11(t，J＝8.7Hz，2H)，7.06(s，1H)，6.99(t，J＝7.0Hz，1H)，6.65-6.51(m，1H)，6.29(dd，J＝15.8，3.6Hz，1H)，4.32(t，J＝9.5Hz，1H)，2.26(d，J＝13.3Hz，3H). 13C?NMR(101MHz，CDCl3)δ＝138.1，138.0，136.7(d，J＝2.4Hz)，135.9(d，J＝5.9Hz)，134.4(d，J＝11.3Hz)，132.1(d，J＝76.3Hz)，131.8(d，J＝79.1Hz)，131.5(d，J＝42.7Hz)，131.2，130.2(d，J＝5.7Hz)，128.4(d，J＝2.0Hz)，128.3(d，J＝29.1Hz)，128.2(d，J＝23.7Hz)，127.9(d，J＝2.3Hz)，127.0(d，J＝1.2Hz)，126.5(d，J＝5.7Hz)，124.5(d，J＝7.1Hz)，123.6(d，J＝1.1Hz)，52.4(d，J＝64.7Hz)，21.4(d，J＝7.6Hz). 31P?NMR(162MHz，CDCl3)δ＝31.43(s).IR(KBr)：v max(cm -1)＝3048，2916，2848，1604，1551，1179，1113，956，836，706，566，512.HRMS(EI)calcd?for?C 29H 27NaOP[M+Na] +：445.1692，Found：445.1693.
P18:(E)-(1,3-bis-(1-naphthyl)-allyl group)-diphenyl phosphate oxygen
White solid, fusing point: 198.5-200.3 DEG C, 65% yield .68%ee[chiral column IC-H (0.46cm x25cm); Normal hexane/Virahol=70/30; Flow velocity=1.0mL/min; Detect wavelength=254nm; t r=13.702 (minor), 23.239 (major) min].
[α] D 20＝+7.1°(c0.5，CHCl 3).
1H?NMR(400MHz，CDCl 3)δ8.26(d，J＝7.1Hz，1H)，8.11(d，J＝8.3Hz，1H)，8.05-7.91(m，2H)，7.81(d，J＝7.9Hz，1H)，7.73(t，J＝8.6Hz，2H)，7.67(d，J＝8.1Hz，1H)，7.62-7.48(m，6H)，7.46(d，J＝6.8Hz，2H)，7.42(d，J＝6.1Hz，2H)，7.38(d，J＝10.8Hz，3H)，7.30(t，J＝7.8Hz，2H)，7.22(d，J＝8.1Hz，1H)，7.13(td，J＝7.9，2.7Hz，2H)，7.07(dd，J＝15.5，3.9Hz，1H)，6.66-6.53(m，1H)，5.39(t，J＝9.6Hz，1H). 13C?NMR(101MHz，CDCl3)δ＝134.5(d，J＝2.6Hz)，134.0，133.4，133.0，132.5，132.4(d，J＝10.9Hz)，132.2(d，J＝4.6Hz)，131.9(d，J＝8.4Hz)，131.7(d，J＝2.6Hz)，131.6，131.5(d，J＝2.7Hz)，131.4(d，J＝2.7Hz)，131.0(d，J＝8.9Hz)，129.2，128.5(d，J＝40.7Hz)，128.4(d，J＝39.5Hz)，128.0(d，J＝14.2Hz)，127.0(d，J＝1.2Hz)，126.5(d，J＝5.7Hz)，124.5(d，J＝7.1Hz)，123.6(d，J＝1.1Hz)，47.0(d，J＝66.1Hz). 31P?NMR(162MHz，CDCl3)δ＝32.44(s).IR(KBr)：v max(cm -1)＝3054，2923，2848，1587，1510，1438，1388，1179，1111，962，801，775，724，694，566，525.HRMS(EI)calcd?for?C 35H 27NaOP[M+Na] +：517.1692，Found：517.1691.
P19:(E)-(1,3-bis-(2-naphthyl)-allyl group)-diphenyl phosphate oxygen
White solid, fusing point: 254.5-255.9 DEG C, 60% yield .95%ee[chiral column IC-H (0.46cm x25cm); Normal hexane/Virahol=70/30; Flow velocity=1.0mL/min; Detect wavelength=254nm; t r=13.180 (minor), 16.565 (major) min].
[α] D 20＝+10.1°(c0.5，CHCl 3).
1H?NMR(400MHz，CDCl 3)δ7.94-7.85(m，1H)，7.80-7.67(m，2H)，7.68-7.60(m，1H)，7.55(d，J＝7.5Hz，1H)，7.51-7.43(m，1H)，7.44-7.37(m，1H)，7.33(d，J＝7.3Hz，1H)，7.25(dd，J＝4.3，3.3Hz，1H)，6.79(ddd，J＝15.9，8.8，7.3Hz，1H)，6.48(dd，J＝15.7，3.6Hz，1H)，4.59(t，J＝9.4Hz，1H). 13C?NMR(101MHz，CDCl3)δ＝134.6(d，J＝2.6Hz)，134.1(d，J＝2.4Hz)，133.6(d，J＝6.1Hz)，133.4，133.0，132.5，132.2(d，J＝5.8Hz)，131.8(d，J＝2.6Hz)，131.7(d，J＝8.5Hz)，131.6(d，J＝2.6Hz)，131.4(d，J＝8.7Hz)，128.4(d，J＝35.9Hz)，128.0(d，J＝49.9Hz)，128.1(d，J＝11.7Hz)，127.6(d，J＝3.4Hz)，127.5(d，J＝3.1Hz)，126.1(d，J＝17.2Hz)，125.9(d，J＝3.9Hz)，125.0(d，J＝7.2Hz)，123.6，52.5(d，J＝64.7Hz). 31P?NMR(162MHz，CDCl3)δ＝31.44(s).IR(KBr)：v max(cm -1)＝3054，2920，2845，1596，1500，1435，1369，1168，1114，962，810，745，721，691，563，540，477.HRMS(EI)calcd?for?C 35H 27NaOP[M+Na] +：517.1692，Found：517.1683.
Embodiment 3
In the present embodiment, the step of the synthetic Phosphorus compound of 1,3-, bis-substituted allyl oxygen is as follows:
(1) press allyl carbonate methyl esters, diphenyl phosphate oxygen, Pd 2(dba) 3and the mol ratio of part is 5: 1: 0.05: 0.1, first above-mentioned allyl carbonate methyl esters, diphenyl phosphate oxygen reaction raw materials are joined in dichloromethane solution, and fully stir, then add Pd 2(dba) 3and part, controlling temperature of reaction is 60 DEG C, reaction 12h, makes crude product;
(2) crude product step (1) being made carries out separating-purifying by column chromatography, and developping agent used is that sherwood oil and methylene dichloride are the mixing solutions of 1: 1 by volume, finally makes the Phosphorus compound of 1,3-, bis-substituted allyl oxygen.
Embodiment 4
In the present embodiment, the step of the synthetic Phosphorus compound of 1,3-, bis-substituted allyl oxygen is as follows:
(1) press allyl carbonate methyl esters, diphenyl phosphate oxygen, Pd 2(dba) 3and the mol ratio of part is 5: 1: 0.05: 0.1, first above-mentioned allyl carbonate methyl esters, diphenyl phosphate oxygen reaction raw materials are joined in tetrahydrofuran solution, and fully stir, then add Pd 2(dba) 3and part, controlling temperature of reaction is 55 DEG C, reaction 12h, makes crude product;
(2) crude product step (1) being made carries out separating-purifying by column chromatography, and developping agent used is that sherwood oil and ether are the mixing solutions of 1: 1 by volume, finally makes the Phosphorus compound of 1,3-, bis-substituted allyl oxygen.
Embodiment 5
In the present embodiment, the step of the synthetic Phosphorus compound of 1,3-, bis-substituted allyl oxygen is as follows:
(1) press allyl carbonate methyl esters, diphenyl phosphate oxygen, Pd 2(dba) 3and the mol ratio of part is 1.2: 1: 0.05: 0.1, first above-mentioned allyl carbonate methyl esters, diphenyl phosphate oxygen reaction raw materials are joined in toluene solution, and fully stir, then add Pd 2(dba) 3and part, controlling temperature of reaction is 25 DEG C, reaction 1h, makes crude product:
(2) crude product step (1) being made carries out separating-purifying by column chromatography, and developping agent used is that sherwood oil and ethyl acetate are the mixing solutions of 1: 1 by volume, finally makes the Phosphorus compound of 1,3-, bis-substituted allyl oxygen.

Claims (7)

1. the Phosphorus compound of 3-bis-substituted allyl oxygen, is characterized in that, the structural formula of this compound is: wherein * is chiral carbon atom, and R is phenyl ring or contains substituent aryl.
2. one kind as claimed in claim 11, the preparation method of the Phosphorus compound of 3-bis-substituted allyl oxygen, is characterized in that, the method is using chirality palladium complex as catalyzer, carry out high enantioselective reactions by allyl carbonate methyl esters, diphenyl phosphate oxygen, specifically comprise the following steps:
(1) diphenyl phosphate oxygen and allyl carbonate methyl esters are joined in organic solvent, fully stir, then add catalyzer, controlling temperature of reaction is 25 DEG C～60 DEG C, and reaction 1～12h, makes crude product;
(2) crude product step (1) being made carries out separating-purifying, i.e. the synthetic Phosphorus compound of 1,3-, bis-substituted allyl oxygen that obtains.
3. according to claim 2 a kind of 1, the preparation method of the Phosphorus compound of 3-bis-substituted allyl oxygen, is characterized in that, the described catalyzer of step (1) is with Pd 2(dba) 3palladium complex with part effect generation.
4. according to the one 1 described in claim 2 or 3, the preparation method of the Phosphorus compound of 3-bis-substituted allyl oxygen, is characterized in that described allyl carbonate methyl esters, diphenyl phosphate oxygen, Pd 2(dba) 3and the mol ratio of part is (1.2～5): 1: 0.05: 0.1.
5. according to claim 2 a kind of 1, the preparation method of the Phosphorus compound of 3-bis-substituted allyl oxygen, is characterized in that, the described organic solvent of step (1) is one or more in toluene, methylene dichloride, tetrahydrofuran (THF).
6. according to the one 1 described in claim 2 or 3, the preparation method of the Phosphorus compound of 3-bis-substituted allyl oxygen, is characterized in that, the structural formula of described diphenyl phosphate oxygen is the structural formula of described allyl carbonate methyl esters is wherein R is phenyl ring or contains substituent aryl, and described part is optics
Pure part, its structural formula is in one.
7. according to claim 2 a kind of 1, the preparation method of the Phosphorus compound of 3-bis-substituted allyl oxygen, is characterized in that, the method for the described separating-purifying of step (2) is one or more in thin-layer chromatography, column chromatography and underpressure distillation.
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CN108774263A (en) * 2018-06-26 2018-11-09 广东工业大学 A kind of synthetic method of allyl oxidation phosphine compound
CN108774263B (en) * 2018-06-26 2020-09-22 广东工业大学 Synthesis method of allyl phosphine oxide compound
CN113861238A (en) * 2021-10-20 2021-12-31 华东师范大学 Method for simultaneously synthesizing secondary/tertiary phosphine oxide compound with phosphine chiral center under catalysis of palladium/chiral ligand
CN113861238B (en) * 2021-10-20 2024-03-12 华东师范大学 Method for synthesizing phosphine chiral center secondary/tertiary phosphine oxide compound through palladium/chiral ligand catalysis
CN114736108A (en) * 2022-04-12 2022-07-12 同济大学 Allyl carbonyl enol compound and synthetic method thereof
CN114736108B (en) * 2022-04-12 2023-10-27 同济大学 Allyl carbonyl enol compound and synthesis method thereof

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