CN104478919A - Method for synthesizing chiral silane compound - Google Patents
Method for synthesizing chiral silane compound Download PDFInfo
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- CN104478919A CN104478919A CN201410655750.2A CN201410655750A CN104478919A CN 104478919 A CN104478919 A CN 104478919A CN 201410655750 A CN201410655750 A CN 201410655750A CN 104478919 A CN104478919 A CN 104478919A
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Abstract
The invention discloses a method for synthesizing a chiral silane compound. The method comprises the step of: with olefin and hydrogenated silicon as raw materials and a chiral FeX2-IPO complex as a catalyst, reacting for 3 minutes to 48 hours to prepare the chiral silane compound in the presence of sodium triethylborohydride, wherein the molar ratio of olefin to hydrogenated silicon to the FeX2-IPO complex to sodium triethylborohydride is 1 to (0.1-10) to (0.0005-0.05) to (0.0015-0.15), and the reaction temperature is (-30)-80 DEG C. The chiral silane compound synthesized the reaction has very high application values in many fields, for instance, the chiral silane compound can be derived to generate chiral silanol and a cyclosilane compound which are widely applied in the material filed as well as chiral 2-hydroxy phenyl ethyl alcohol compounds or chiral benzofuran compounds which widely exist in the biological medicine field.
Description
Technical field
Present method relates to a kind of method of synthesis of chiral silane compound, especially relates to a kind of synthetic method of optically active silane compound.
Background technology
In recent years, transition metal-catalyzed reaction is widely used at material, chemical industry, pharmaceutical field, but due to the problem of metal residual, transition-metal catalyst especially has many restrictions at pharmaceutical field, and the problem that the reaction of iron catalysis just can avoid toxic heavy metal residual, the reaction therefore developing efficient iron catalysis has great meaning for pharmaceutical synthesis field.
The most important semiconductor material of silicon materials, hydrosilation reaction is the important channel obtaining organosilicon material.Hydrosilation reaction has been widely used in preparation at present containing a series of silicoorganic compound [a) K.Tamao such as carbon-to-carbon double bond, carbon-to-carbon three key, carbon-oxygen double bond, carbon-nitrogen double bond, carbon-nitrogen three key, nitrogen-nitrogen double bond and nitrogen-oxygen keys, N.Ishida, T.Tanaka, M.Kumada, Organometallics 1983,2,1694; B) I.Fleming, R.Henning, H.Plaut, J.Chem.Soc.Chem.Commun.1984,29.].Hydrosilation reaction also does [a) Y.Hatanaka, T.Hiyama, J.Org.Chem.1988,53,918 such as protecting group and reductive agent in synthesis of natural organic compound; B) S.E.Denmark, C.S.Regens, Acc.Chem.Res.2008,41,1486.].
But the silica reagent how efficiently preparing chirality is focus and the difficult point of organic chemistry filed research, 1976, and Kumada has developed Asymmetric hydrosilylation [Yamamoto, the K. of alkene always; Hayashi, T.; Zembayashi, M.; Kumada, M.J.Organomet.Chem.1976,118,161], but enantio-selectivity lower (0.6-20.9%ee).Had again the Asymmetric hydrosilylation of research group to alkene to attempt and improve afterwards, but effect is not very desirable, the limitation of substrate is very large, and enantio-selectivity is also lower, needs to use catalyzer [a] Tamao, the K. such as noble metal rhodium simultaneously; Tohma, T.; Inui, N.; Nakayama, O.; Ito, Y.Tetrahedron Lett.1990,31,7333.b) Bergens, S.H.; Noheda, P.; Whelan, J.; Bosnich, B.J.Am.Chem.Soc.1992,114,2121.c) Fu, P.-F.; Brard, L.; Li, Y.; Marks, T.J.J.Am.Chem.Soc.1995,117,7157.].
Therefore, the hydrosilation reaction synthesis of chiral silane compound of the alkene of the iron catalysis of development high-level efficiency highly selective has great meaning, especially has broad application prospects at medicine and Material Field.
Summary of the invention
The present invention is just for the improvement that the deficiencies in the prior art part is made, and providing a kind of method of effective synthesizing silane compound, is by chirality FeX
2the hydrosilation reaction of-IPO complex catalysis alkene and silicon hydrogen, substrate spectrum is wide, be applicable to aliphatics, the alkene of aromatic alkene and large steric hindrance, the method for the silane compound of high-level efficiency high (productive rate is generally more than 90%) enantio-selectivity ground synthesis of optically active (productive rate is generally 90%).
The present invention is achieved through the following technical solutions:
The invention discloses a kind of method of synthesis of chiral silane compound, with alkene and silicon hydrogen for raw material, with chirality FeX
2-IPO complex compound is catalyzer, under sodium triethylborohydride exists, reacts 3 minutes-48 hours obtained chirality silane compounds, described alkene, silicon hydrogen, FeCl
2the mol ratio of-IPO complex compound, sodium triethylborohydride is 1:0.1-10:0.0005-0.05:0.0015-0.15; Temperature of reaction is-30 DEG C ~ 80 DEG C;
The structural formula of described alkene is
r
1≠ R
2;
The structural formula of described pinacol borine is Ph
2siH
2or Ph
3siH or PhSiH
3, Et
2siH
2, (EtO)
3siH, Et
3any one in SiH; ;
Wherein, R
1, R
2the optional C from comprising cycloalkyl
1-C
16alkyl, replacement aryl
in any one, wherein R
3, R
4, R
5, R
6, R
7optional from H, halogen, C
1-C
16alkyl, C
1-C
16-oxyl, any one in sulfenyl, X is F, Cl, Br, I, OAc, CF
3sO
3in any one, R
3for Ph
2h, PhH
2, Et
3, (EtO)
3, Et
2any one in H, the product of reaction can obtain the silicon alcohol compound of chirality by derivatize, can be widely used in Material Field; The benzo ring silane compound of chirality, can be widely used in Material Field; The 2-hydroxypropiophenone alcohol compound of chirality, can be widely used in pharmaceutical field; The benzofuran compounds of chirality, can widespread use biomedicine field.
As improving further, FeX of the present invention
2-IPO complex compound is chiral complex, and described product silane compounds is optically active, and its structural formula is
wherein * represents chiral carbon atom R
1, R
2the optional C from comprising cycloalkyl
1-C
16alkyl, replacement aryl
r
3for Ph
2h, PhH
2, Et
3, (EtO)
3, Et
2any one in H.
As improving further, FeX of the present invention
2the structural formula of-IPO complex compound is optically pure following compound or its enantiomorph or raceme, R
8optional from C
1-C
16alkyl, naphthyl, replacement aryl, benzyl:
X is F, Cl, Br, I, OAc, CF
3sO
3in any one.
As improving further, the participation of organic solvent is had in described synthetic method of the present invention, described organic solvent is any one in benzene, tetracol phenixin, toluene, tetrahydrofuran (THF), ether, methylene dichloride, acetonitrile, dioxane, sherwood oil, hexanaphthene, normal hexane, ethyl acetate, trichloromethane, N, N-diformamide.
As improving further, in described synthetic method of the present invention, do not add any solvent.
As improving further, described alkene, pinacol borine, FeX of the present invention
2the mol ratio of-IPO complex compound, sodium triethylborohydride is, 1:0.5-2:0.005-0.05:0.015-0.15, and temperature of reaction is-10 DEG C ~ 60 DEG C, and the reaction times is 30 minutes-12 hours.
As improving further, alkene of the present invention, silicon hydrogen, FeX
2the mol ratio of-IPO complex compound, sodium triethylborohydride is 1:1:0.05:0.15, and temperature of reaction is 25 DEG C, and the reaction times is 1 hour.
As improving further, in described synthetic method of the present invention, temperature of reaction is-30 DEG C ~ 80 DEG C.
Be through recrystallization, thin-layer chromatography, column chromatography or underpressure distillation as the product improving gained to be further separated and to form.
As improving further, synthesized chirality silane compound can obtain the silicon alcohol compound of chirality through derivative reaction, can be widely used in Material Field; The benzo ring silane compound of chirality, can be widely used in Material Field; The 2-hydroxypropiophenone alcohol compound of chirality, can be widely used in pharmaceutical field; Or the benzofuran compounds of chirality, can widespread use biomedicine field.
Beneficial effect of the present invention is as follows:
Present approach provides a kind of effective by FeX
2-IPO complex compound especially chirality FeX
2-IPO complex compound is catalyzer, by the method for alkene and the silicon hydrogen high-level efficiency high antimer optionally silane compound of synthesis of optically active.Compared with the conventional method, the method is applicable to the alkene (aliphatics of number of different types, the alkene of aromatic series and large steric hindrance), reaction conditions gentleness (can occur under room temperature), reactive behavior good (can complete for general 1 hour), easy and simple to handle, Atom economy high (100%).In addition, the catalyzer reacting used is the complex compound of iron, without the need to adding of other any poisonous transition metal (as ruthenium, rhodium, palladium etc.) salts, and the productive rate of reaction is also better, be generally 80% ~ 98%, enantio-selectivity is also higher, is generally 80% ~ 99%.And, react the chirality silane compound obtained and can have very large using value in a lot of field, as obtained in Material Field widespread use chirality silanol by derivatize, cyclosilane compound, the 2-hydroxypropiophenone alcohol compound of chirality extensively existed at biomedicine field or the benzofuran compounds of chirality.
Embodiment
Method of the present invention is a kind of effectively by the method for alkene and silicon hydrogen synthesizing silane compound.The method uses FeX
2-IPO complex compound is as catalyzer.Especially with the FeX of chirality
2-IPO complex compound is as can by the silane compound of alkene and silicon hydrogen high-level efficiency high antimer optionally synthesis of optically active during catalyzer.
The general molecular formula of the silane compound synthesized by the inventive method is:
as use chirality FeX
2when-IPO complex compound is as catalyzer, synthesized silane compound is optically active, and its general formula is
wherein * represents chiral carbon atom.R
1, R
2the optional C from comprising cycloalkyl
1-C
16alkyl, naphthyl, replacement aryl
wherein R
3, R
4, R
5, R
6, R
7optional from H, halogen, C
1-C
16alkyl, C
1-C
16-oxyl, amido or substituted aryl, R
3for Ph
2h, PhH
2, Et
3, (EtO)
3, Et
2any one in H.Above-mentioned halogen comprises F, Cl, Br or I, and above-mentioned alkyl can be alkyl, cycloalkyl, benzyl.
Silane compound of the present invention is with alkene and silicon hydrogen for raw material, under sodium triethylborohydride exists, in organic solvent or without the need to solvent, with FeX
2-IPO complex compound is especially with FeX
2-IPO complex compound obtains as catalyst reaction, can be represented by the formula:
The structural formula of alkene is:
wherein, R
1, R
2as previously mentioned; The structural formula of silicon hydrogen is Ph
2siH
2or Ph
3siH or PhSiH
3, Et
2siH
2, (EtO)
3siH, Et
3any one in SiH; The general structure of catalyzer is (be any optically pure structure or its enantiomorph or raceme, do not limit by diagram)
R
8optional from C
1-C
16alkyl, naphthyl, replacement aryl, benzyl.
Described alkene, silicon hydrogen, FeX
2the mol ratio of-IPO complex compound, sodium triethylborohydride is 1:0.1-10:0.0005-0.05:0.0015-0.3, further 1:0.5-2:0.005-0.05:0.015-0.15; Especially the mol ratio of recommendation response is: alkene, silicon hydrogen, FeX
2the mol ratio of-IPO complex compound, sodium triethylborohydride is 1:1:0.05:0.15.Temperature of reaction is recommended as-30 DEG C ~ 80 DEG C, recommends-10 DEG C ~ 60 DEG C further, especially recommends 25 DEG C.Reaction times is recommended as 3 minutes-48 hours, recommends 30 minutes-12 hours further, especially recommends 1 hour.Wherein, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8as previously mentioned.
The alkyl mentioned in the present invention, all recommends carbon number to be the group of 1 ~ 16, further recommends carbon number to be 1 ~ 10, especially to recommend carbon number to be 1 ~ 6.The cycloalkyl that the present invention mentions, all recommends carbon number to be the group of 3 ~ 16, further recommends carbon number to be 3 ~ 10, especially to recommend carbon number to be 3 ~ 6.The aryl that the present invention mentions, all refers to phenyl, naphthyl and the heteroaryl containing N, O, S.
The reaction of the inventive method can be carried out under solvent-free, also can carry out in polarity or non-polar solvent, as benzene, tetracol phenixin, toluene, tetrahydrofuran (THF), ether, methylene dichloride, acetonitrile, dioxane, sherwood oil, hexanaphthene, normal hexane, ethyl acetate, trichloromethane, N, N-diformamide etc.
The inventive method can be separated by recrystallization, thin-layer chromatography, column chromatography or underpressure distillation.Present approach provides the silane compound that some are new
synthetic method.
Below by specific embodiment, technical scheme of the present invention is illustrated further:
Embodiment 1: chirality FeX
2the alkene of-IPO complex catalysis and the hydrosilation reaction of silicon hydrogen
At-30 DEG C, in the reaction tube of a drying, add (chirality) FeX
2-IPO complex compound (0.01mmol), alkene (1mmol), silicon hydrogen (1mmol), ether (1mL), sodium triethylborohydride (0.03mmol), then at room temperature stirs column chromatography for separation after 1 hour and obtains product.
P1：(S)-(-)-diphenyl(2-phenylpropyl)silane
(or its enantiomorph)
Oily liquids, 98% productive rate, [α]
20 d=-22.8 (c 1.0, CHCl
3), 90.9%ee;
1h NMR (400.1 MHz, CDCl
3): δ 7.60-7.46 (m, 4H), 7.42-7.29 (m, 6H), 7.28-7.20 (m, 2H), 7.20-7.10 (m, 3H), 4.77 (t, J=3.6 Hz, 1H), 3.02-2.88 (m, 1H), 1.65-1.48 (m, 2H), 1.31 (d, 3H);
13cNMR (100.6 MHz, CDCl
3): δ 149.0,135.1 (d, J=5.8 Hz), 134.5 (d, J=19.0 Hz), 129.5 (d, J=3.1 Hz), 128.3,127.9,126.6,125.9,36.2,25.2,22.6; HRMS (EI) calculated for [C
21h
22si]
+requires m/z 302.1491, found m/z 302.1487.
P2：(S)-(-)-diphenyl(2-phenylbutyl)silane
Oily liquids, 96% productive rate, [α]
20 d=-24.4 (c 0.99, CHCl
3), 93.7%ee, determined by HPLC, HPLC conditions:Chiralcel OJ-H, n-hexane/i-PrOH=98/2,0.5 mL/min, n=220 nm, t
r10.3 (major), 14.6 (minor);
1h NMR (400.1 MHz, CDCl
3): δ 7.55-7.47 (m, 2H), 7.47-7.41 (m, 2H), 7.40-7.26 (m, 6H), 7.25-7.19 (m, 2H), 7.18-7.05 (m, 3H), 4.65 (t, J=3.6 Hz, 1H), 2.70-2.57 (m, 1H), 1.84-1.69 (m, 1H), 1.69-1.66 (m, 2H), 1.55-1.42 (m, 1H), 0.71 (t, J=7.2 Hz, 3H);
13c NMR (100.6 MHz, CDCl
3): δ 146.6,135.1 (d, J=16.6 Hz), 134.6 (d, J=4.6 Hz), 129.4 (d, J=10.5 Hz), 128.2,127.9 (d, J=7.4 Hz), 127.5,125.9,43.6,32.4,20.7,12.1;
29si NMR (79 MHz, CDCl
3): δ-15.5; HRMS (EI) calculated for [C
22h
24si]
+requires m/z 316.1647, found m/z 316.1652.
P3：(S)-(-)-diphenyl(2-(p-tolyl)propyl)silane
Oily liquids, 87% productive rate, [α]
20 d=-28.7 (c 1.02, CHCl
3), 93.6%ee,
1h NMR (400.1 MHz, CDCl
3): δ 7.60-7.45 (m, 4H), 7.42-7.27 (m, 6H), 7.05 (s, 4H), 4.77 (t, J=3.6 Hz, 1H), 3.00-2.85 (m, 1H), 2.30 (s, 3H), 1.62-1.44 (m, 2H), 1.29 (d, J=6.8 Hz, 3H);
13cNMR (100.6 MHz, CDCl
3): δ 146.0,135.3,135.1 (d, J=5.5 Hz), 134.6 (d, J=20.1Hz), 129.4 (d, J=5.0 Hz), 129.0,127.9 (d, J=1.6 Hz), 126.4,35.8,25.3,22.7,21.0; HRMS (EI) calculated for [C
22h
24si]
+requires m/z 316.1647, found m/z 316.1650.
P4:(S)-(-)-diphenyl(2-(m-tolyl)propyl)silane.
Oily liquids, 92% productive rate, [α]
20 d=-18.9 (c 1.04, CHCl
3), 91.6%ee,
1h NMR (400.1 MHz, CDCl
3): δ 7.57-7.46 (m, 4H), 7.42-7.27 (m, 6H), 7.18-7.08 (m, 1H), 7.02-6.92 (m, 3H), 4.78 (t, J=4.0 Hz, 1H), 2.98-2.85 (m, 1H), 2.29 (s, 3H), 1.61-1.47 (m, 2H), 1.30 (d, J=6.8 Hz, 3H);
13c NMR (100.6 MHz, CDCl
3): δ 148.9,137.8,135.1 (d, J=5.2Hz), 134.6 (d, J=22.3 Hz), 129.4 (d, J=3.2 Hz), 128.2,127.9,127.4,126.6,123.6,36.1,25.1,22.6,21.4; HRMS (EI) calculated for [C22H24Si]+requires m/z 316.1647, found m/z 316.1650.
P5:(S)-(-)-diphenyl(2-(o-tolyl)propyl)silane.
Oily liquids, 96% productive rate, [α]
20 d=-0.2 (c 1.0, CHCl
3), 98.3%ee,
1h NMR (400.1 MHz, CDCl
3): δ 7.56-7.47 (m, 4H), 7.41-7.26 (m, 7H), 7.20-7.11 (m, 1H), 7.09-7.02 (m, 2H), 4.80 (t, J=4.0 Hz, 1H), 3.25-3.11 (m, 1H), 2.08 (s, 3H), 1.62-1.45 (m, 2H), 1.27 (d, J=6.8 Hz, 3H);
13c NMR (100.6 MHz, CDCl
3): δ 147.1,135.0 (d, J=3.8 Hz), 134.6 (d, J=6.2 Hz), 134.4,130.1,129.5,127.9,126.2,125.5,125.3,30.8,24.3,21.8,19.2; HRMS (EI) calculated for [C
22h
24si]
+requires m/z 316.1647, found m/z316.1648.
P6:(S)-(-)-(4-(1-(diphenylsilyl)propan-2-yl)phenoxy)triisopropylsilane
Oily liquids, 88% productive rate, [α]
20 d=-8.6 (c 1.02, CHCl
3), 93.8%ee,
1h NMR (400.1 MHz, CDCl
3): δ 7.57-7.44 (m, 4H), 7.41-7.28 (m, 6H), 6.98 (d, J=8.2 Hz, 2H), 6.75 (d, J=8.4 Hz, 2H), 4.73 (t, J=3.8 Hz, 1H), 2.95-2.81 (m, 1H), 1.59-1.44 (m, 2H), 1.34-1.18 (m, 6H), 1.09 (d, J=7.2 Hz, 18H);
13c NMR (100.6 MHz, CDCl
3): δ 154.0,141.3,135.1 (d, J=9.1 Hz), 134.7 (d, J=8.1 Hz), 129.4 (d, J=2.0 Hz), 127.9,127.3,119.5,35.4,25.5,22.8,17.9,12.7; HRMS (EI) calculated for [C
30h
42oSi
2]
+requires m/z474.2744, found m/z 47432745.
P7:(S)-(-)-(2-(4-fluorophenyl)propyl)diphenylsilane
Oily liquids, 95% productive rate, [α]
20 d=-18.2 (c 0.96, CHCl
3), 88.6%ee,
1h NMR (400.1 MHz, CDCl
3): δ 7.59-7.44 (m, 4H), 7.42-7.26 (m, 6H), 7.14-7.04 (m, 2H), 6.97-6.85 (m, 2H), 4.75 (t, J=3.8 Hz, 1H), 3.00-2.87 (m, 1H), 1.59-1.44 (m, 2H), (1.29 d, J=6.8Hz, 3H);
13c NMR (100.6 MHz, CDCl
3): δ 161.2 (d, J=243.7 Hz), 144.4 (d, J=2.6Hz), 135.0 (d, J=7.4 Hz), 134.3 (d, J=15.2 Hz), 129.5 (d, J=5.4 Hz), 128.0 (d, J=1.6 Hz), 127.9 (d, J=4.2 Hz), 114.9 (d, J=21.0 Hz), 35.6,25.5,22.7;
19f NMR (CDCl
3, 376 MHz): δ-117.5; HRMS (EI) calculated for [C
21h
21fSi]
+requires m/z320.1397, found m/z 320.1396.
P8:(S)-(+)-(2-(2-methoxyphenyl)propyl)diphenylsilane.
Oily liquids, 97% productive rate, [α]
20 d=+7.1 (0.99, CHCl
3), 93.6%ee,
1h NMR (400.1 MHz, CDCl
3): δ 7.59-7.45 (m, 4H), 7.41-7.26 (m, 6H), 7.24-7.17 (m, 1H), 7.16-7.07 (m, 1H), 6.94-6.84 (m, 1H), 6.75 (d, J=8.0 Hz, 1H), 4.79 (t, J=3.8 Hz, 1H), 3.68 (s, 3H), 3.51-3.38 (m, 1H), 1.67-1.55 (m, 1H), 1.53-1.40 (m, 1H), 1.29 (d, J=6.8 Hz, 3H);
13cNMR (100.6 MHz, CDCl
3): δ 156.5,137.0,135.1 (d, J=8.4 Hz), 134.8,129.3,127.8,126.6,126.5,120.5,110.3,55.0,28.7,23.2,21.4; HRMS (EI) calculated for [C
22h
24oSi]
+requires m/z 332.1596, found m/z 332.1600.
P9:(S)-(+)-(2-(2-bromophenyl)propyl)diphenylsilane.
Oily liquids, 94% productive rate, [α]
20 d=+0.8 (0.99, CHCl
3), 95.0%ee,
1h NMR (400.1 MHz, CDCl
3): δ 7.58-7.47 (m, 6H), 7.46-7.40 (m, 1H), 7.40-7.28 (m, 6H), 7.24-7.17 (m, 1H), 4.88 (t, J=3.6 Hz, 1H), 3.52-3.40 (m, 1H), 1.65-1.50 (m, 2H), (1.29 d, J=6.4Hz, 3H);
13c NMR (100.6 MHz, CDCl
3): δ 148.6,135.0 (d, J=3.7 Hz), 134.2 (d, J=61.8 Hz), 132.0,129.6,128.0 (d, J=3.7 Hz), 127.5,125.7,125.42,125.36,31.0,24.9,22.7; HRMS (EI) calculated for [C
21h
21brSi]
+requires m/z 380.0596, found m/z380.0599.
P10:(S)-(-)-(2-(naphthalen-2-yl)propyl)diphenylsilane.
Oily liquids, 88% productive rate, [α]
20 d=-41.0 (c 1.05, CHCl
3), 90.1%ee,
1h NMR (400.1 MHz, CDCl
3): δ 7.81-7.69 (m, 3H), 7.57-7.47 (m, 5H), 7.46-7.26 (m, 9H), 4.78 (t, J=4.0Hz, 1H), 3.19-3.06 (m, 1H), 1.72-1.56 (m, 2H), 1.39 (d, J=6.8 Hz, 3H);
13c NMR (100.6 MHz, CDCl
3): δ 146.3,135.1 (d, J=8.3 Hz), 134.5 (d, J=19.9 Hz), 133.6,132.2,129.5 (d, J=6.0 Hz), 128.0,127.9,127.6,127.5,125.8,125.5,125.1,124.6,36.3,25.1,22.4; HRMS (EI) calculated for [C
25h
24si]
+requires m/z 352.1647, foundm/z 352.1649.
P11:(S)-(+)-(2-(naphthalen-1-yl)propyl)diphenylsilane.
Oily liquids, 99% productive rate, [α]
20 d=+56.8 (c 1.0, CHCl
3), >99%ee,
1h NMR (400.1 MHz, CDCl
3): δ 7.90-7.78 (m, 2H), 7.66 (d, J=7.8 Hz, 1H), 7.62-7.53 (m, 2H), 7.53-7.26 (m, 12H), 4.92 (t, J=3.8 Hz, 1H), 3.87-3.74 (m, 1H), 1.81-1.71 (m, 1H), 1.63-1.56 (m, 1H), 1.46 (d, J=6.8 Hz, 3H);
13c NMR (100.6 MHz, CDCl
3): δ 145.2,135.1 (d, J=9.8 Hz), 134.4 (d, J=13.7 Hz), 133.9,131.0,129.6 (d, J=10.4 Hz), 128.9,128.0,127.9,126.4,125.6,125.2,123.1,122.3,30.1,23.9,22.3; HRMS (EI) calculated for [C
25h
24si]
+requires m/z 352.1647, found m/z 352.1651.
P12:(S)-(-)-(2-cyclohexyl-2-phenylethyl)diphenylsilane.
Oily liquids, 96% productive rate, [α]
20 d=-31.8 (c 0.98, CHCl
3), 96.1%ee,
1h NMR (400.1 MHz, CDCl
3): δ 7.52-7.43 (m, 2H), 7.42-7.22 (m, 8H), 7.22-7.09 (m, 3H), 7.04-6.97 (m, 2H), 4.50-4.40 (m, 1H), 2.55-2.41 (m, 1H), 1.99-1.86 (m, 1H), 1.82-1.66 (m, 2H), 1.65-1.52 (m, 2H), 1.50-1.36 (m, 3H), 1.24-1.12 (m, 1H), 1.10-0.96 (m, 2H), 0.94-0.79 (m, 1H), 0.79-0.64 (m, 1H);
13c NMR (100.6 MHz, CDCl
3): δ 144.9,135.0 (d, J=29.9 Hz), 134.8 (d, J=47.8 Hz), 129.3 (d, J=17.2 Hz), 128.6,127.9,127.8 (d, J=4.2 Hz), 125.9,47.9,45.3,31.3,30.5,26.6,26.48,26.46,16.7; HRMS (EI) calculated for [C
26h
30si]
+requires m/z 370.2117, found m/z 370.2121.
P13:(R)-(-)-tert-butyl((5-(diphenylsilyl)-4-phenylpentyl)oxy)dimethylsilane.
Oily liquids, 93% productive rate, [α]
20 d=-14.8 (c 1.03, CHCl
3), 97.0%ee,
1h NMR (400.1 MHz, CDCl
3): δ 7.54-7.46 (m, 2H), 7.46-7.41 (m, 2H), 7.41-7.25 (m, 6H), 7.25-7.18 (m, 2H), 7.17-7.11 (m, 1H), 7.11-7.04 (m, 2H), 4.65 (t, J=3.6 Hz, 1H), 3.46 (t, J=6.6 Hz, 2H), 2.77-2.65 (m, 1H), 1.86-1.73 (m, 1H), 1.71-1.45 (m, 3H), 1.41-1.20 (m, 2H), 0.85 (s, 9H),-0.03 (d, J=1.6 Hz, 6H);
13c NMR (100.6 MHz, CDCl
3): δ 146.6,135.1 (d, J=16.1 Hz), 134.5 (d, J=4.8 Hz), 129.4 (d, J=11.1 Hz), 128.2, (127.9 d, J=7.7Hz), 127.5,126.0,63.0,41.7,35.7,30.8,26.0,21.3,18.3 ,-5.3; HRMS (EI) calculatedfor [C
29h
40oSi
2]
+requires m/z 460.2618, found m/z 460.2618.
P14:(S)-(-)-(3-(4-methoxyphenyl)-2-methylpropyl)diphenylsilane.
Oily liquids, 92% productive rate, [α]
20 d=-11.8 (c 1.0, CHCl
3), 44.8%ee,
1h NMR (400.1 MHz, CDCl
3): δ 7.56-7.45 (m, 4H), 7.41-7.29 (m, 6H), 6.97 (d, J=8.4 Hz, 2H), 6.79 (d, J=8.4 Hz, 2H), 4.94 (m, 1H), 3.77 (s, 3H), 2.62-2.63 (m, 1H), 2.48-2.39 (m, 1H), 2.00-1.86 (m, 1H), 1.35-1.24 (m, 1H), 1.07-0.98 (m, 1H), 0.93 (d, J=6.6 Hz, 3H);
13cNMR (100.6 MHz, CDCl
3): δ 157.7,135.1 (d, J=8.0 Hz), 134.8 (d, J=43.9 Hz), 133.3,130.1,129.4 (d, J=1.6 Hz), 127.9,113.5,55.2,45.6,32.0,22.3,19.9; HRMS (EI) calculated for [C
23h
26oSi]
+requires m/z 346.1753, found m/z 346.1750.
Embodiment 2: product oxidative synthesis silanol compounds (application example)
Silicon hydride (1mmol) is added, trifluoroacetophenone (0.1mmol), tBuOH (0.5mL), saturated NaHCO in 20mL reaction tubes
3solution (0.5mL), CH
3cN (0.08mL), 30%H
2o
2the aqueous solution (0.11mL), stirred at ambient temperature is separated after 12 hours and obtains silanol product.(S)-(-)-(3-methyl-2-phenylbutyl) diphenylsilanol: colourless oil liquid, 94% productive rate, OpticalRotation:[α]
20 d=-23.8 (c 0.99, CHCl
3), 98.1%ee,
1h NMR (400.1 MHz, CDCl
3): δ 7.60-7.49 (m, 2H), 7.49-7.43 (m, 2H), 7.43-7.14 (m, 9H), 7.08-6.99 (m, 2H), 2.55-2.43 (m, 1H), 1.86-1.74 (m, 1H), 1.69 (dd, J=15.0,3.6 Hz, 1H), 1.55-1.43 (m, 1H), 1.21 (s, 1H), 0.95 (d, J=6.4 Hz, 3H), 0.67 (d, J=6.4 Hz, 3H);
13c NMR (100.6MHz, CDCl
3): δ 145.4,136.5 (d, J=67.6 Hz), 133.9 (d, J=22.5 Hz), 129.6,128.3 (d, J=9.5 Hz), 127.8,127.7,126.4,48.2,35.8,20.7,20.4,19.8; HRMS (EI) calculatedfor [C
23h
26oSi]
+requires m/z 346.1753, found m/z 346.1752.
Embodiment 3: product derivatize synthesis benzo ring silane compound (application example)
Silane compound (0.5mmol) is added, [Ir (OMe) (cod)] in 10mL reaction tubes
2(0.01mmol), 4,4-, bis--tertiary butyl dipyridyl (0.02mmol), 2-norbornylene (0.6mmol), THF (2.5mL), 80 DEG C of reactions are separated after 12 hours and obtain dihydrobenzosiloles product.(S)-(-)-3-methyl-1,1-diphenyl-2,3-dihydro-1H-benzo [b] silole:89% productive rate, [α]
20 d=-8.6 (c 1.04, CHCl
3), 91.5%ee,
1h NMR (400.1 MHz, CDCl
3): δ 7.66 (d, J=7.2 Hz, 1H), 7.64-7.58 (m, 2H), 7.58-7.49 (m, 2H), 7.45-7.29 (m, 8H), 7.26-7.21 (m, 1H), 3.51-3.37 (m, 1H), 1.79 (dd, J=15.2,8.0 Hz, 1H), 1.38 (d, J=6.8 Hz, 3H), 1.17 (dd, J=15.0,6.0 Hz, 1H);
13c NMR (100.6 MHz, CDCl
3): δ 158.9,136.1,135.5 (d, J=33.6 Hz), 135.1 (d, J=7.8 Hz), 133.2,130.1,129.5 (d, J=1.8 Hz), 127.9,126.1,124.9,38.4,25.0,20.6; HRMS (EI) calculated for [C
21h
20si]
+requires m/z 300.1334, found m/z 300.1337.
Embodiment 4: product derivatize synthesis 2-hydroxypropiophenone alcohol compound (application example)
Under ice bath, potassium tert.-butoxide (1.8mmol) is added in 10mL reaction tubes, THF (2mL), peroxy tert-butyl alcohol (1.8mmol), stir the benzo ring silane compound (0.3mmol) adding after ten minutes and synthesized by silane compound, TBAF (1.8mmol), 70 DEG C of reactions are separated after 12 hours and obtain 2-hydroxypropiophenone alcohol product.(S)-(+)-2-(1-hydroxypropan-2-yl) phenol: oily liquids, 86%yield, [α]
20 d=+7.4 (c 1.5, CHCl
3), 91.5%ee,
1h NMR (400.1 MHz, CDCl
3): δ 7.15-7.05 (m, 2H), 6.94-6.79 (m, 2H), 5.25 (br, 2H), 3.85 (dd, J=10.0,4.0 Hz, 1H), 3.72-3.62 (m, 1H), 3.30-3.15 (m, 1H), 1.28 (d, J=7.2 Hz, 3H);
13c NMR (100.6 MHz, CDCl
3): δ 154.6,130.6,127.8,127.7,120.6,116.8,69.0,36.7,15.7; HRMS (EI) calculated for [C
21h
20si]
+requires m/z 152.0837, found m/z 152.0838.
Embodiment 5: product derivatize synthesis benzofuran compounds (application example)
2-hydroxypropiophenone alcohol compound (0.4mmol) is added in 10mL reaction tubes, THF (2mL), triphenylphosphine (0.48mmol), diisopropyl azo-2-carboxylic acid (0.6mmol) stirring at room temperature is separated after 2 hours and obtains benzofurans product.(S)-(+)-3-methyl-2,3-dihydrobenzofuran:83% productive rate, [α]
20 d=+10.4 (c 1.1, CHCl
3), 91.5%ee,
1h NMR (400.1 MHz, CDCl
3): δ 7.12 (d, J=7.2 Hz, 2H), 6.94-6.85 (m, 2H), 3.99-3.89 (m, 1H), 3.75-3.69 (m, 1H), 3.26-3.21 (m, 1H), 1.31 (d, J=7.2 Hz, 3H);
13c NMR (100.6 MHz, CDCl
3): δ 159.6,128.1,127.1,125.1,120.3,109.4,79.6,37.2,21.9; HRMS (EI) calculated for [C
21h
20si]
+requires m/z 134.0732, found m/z 134.0730.
Finally, it is also to be noted that what enumerate above is only specific embodiments of the invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (9)
1. a method for synthesis of chiral silane compound, is characterized in that with alkene and silicon hydrogen for raw material, with chirality FeX
2-IPO complex compound is catalyzer, under sodium triethylborohydride exists, reacts 3 minutes-48 hours obtained chirality silane compounds, described alkene, silicon hydrogen, FeCl
2the mol ratio of-IPO complex compound, sodium triethylborohydride is 1:0.1-10:0.0005-0.05:0.0015-0.15, and temperature of reaction is-30 DEG C ~ 80 DEG C;
The structural formula of described alkene is
r
1≠ R
2;
The structural formula of described silicon hydrogen is Ph
2siH
2or Ph
3siH or PhSiH
3, Et
2siH
2, (EtO)
3siH, Et
3any one in SiH;
Wherein, R
1, R
2the optional C from comprising cycloalkyl
1-C
16alkyl, replacement aryl,
in any one, wherein R
3, R
4, R
5, R
6, R
7optional from H, halogen, C
1-C
16alkyl, C
1-C
16-oxyl, any one in sulfenyl, X is F, Cl, Br, I, OAc, CF
3sO
3in any one, the product of-reaction can obtain the silicon alcohol compound of chirality, the benzo ring silane compound of chirality, the 2-hydroxypropiophenone alcohol compound of chirality, the benzofuran compounds of chirality by derivatize.
2. the method for synthesis of chiral silane compound according to claim 1, is characterized in that, described FeCl
2-IPO complex compound is chiral complex, and described product silane compounds is optically active, and its structural formula is
wherein * represents chiral carbon atom R
1, R
2as claimed in claim 1, R
3for Ph
2h, PhH
2, Et
3, (EtO)
3, Et
2any one in H.
3. the method for synthesis of chiral silane compound according to claim 1 and 2, is characterized in that, described FeX
2the structural formula of-IPO complex compound is optically pure following compound or its enantiomorph or raceme, R
8optional from C
1-C
16alkyl, naphthyl, replacement aryl, benzyl:
X is F, Cl, Br, I, OAc, CF
3sO
3in any one.
4. the method for synthesis of chiral silane compound according to claim 1, it is characterized in that, the participation of organic solvent is had in described synthetic method, described organic solvent is any one in benzene, tetracol phenixin, toluene, tetrahydrofuran (THF), ether, methylene dichloride, acetonitrile, dioxane, sherwood oil, hexanaphthene, normal hexane, ethyl acetate, trichloromethane, N, N-diformamide.
5. the method for synthesis of chiral silane compound according to claim 1, is characterized in that, does not add any solvent in described synthetic method.
6. the method for the synthesis of chiral silane compound according to claim 1 or 2 or 4 or 5, is characterized in that, described alkene, silicon hydrogen, FeX
2the mol ratio of-IPO complex compound, sodium triethylborohydride is 1:0.5-2:0.005-0.05:0.015-0.15, and temperature of reaction is-10 DEG C ~ 60 DEG C, and the reaction times is 30 minutes-12 hours.
7. the method for synthesis of chiral silane compound according to claim 6, is characterized in that, described alkene, silicon hydrogen, FeX
2the mol ratio of-IPO complex compound, sodium triethylborohydride is 1:1:0.05:0.15, and temperature of reaction is 25 DEG C, and the reaction times is 1 hour.
8. the method for synthesis of chiral silane compound according to claim 6, is characterized in that, the product of gained is through recrystallization, thin-layer chromatography, column chromatography or underpressure distillation and is separated and forms.
9. the method for the synthesis of chiral silane compound according to claim 1 or 2 or 4 or 5 or 7 or 8, it is characterized in that, synthesized chirality silane compound can obtain the benzofuran compounds of the silicon alcohol compound of chirality, the benzo ring silane compound of chirality, the 2-hydroxypropiophenone alcohol compound of chirality or chirality through derivative reaction.
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Cited By (6)
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| CN106565764A (en) * | 2016-10-31 | 2017-04-19 | 浙江大学 | Method for synthesizing alpha-chiral silane compound through one-pot method |
| CN107235995A (en) * | 2017-06-09 | 2017-10-10 | 浙江大学 | A kind of chiral two silane compound and its synthetic method and application |
| CN108440591A (en) * | 2018-03-20 | 2018-08-24 | 浙江大学 | A kind of synthetic method of chiral two silane compound |
| CN109111333A (en) * | 2018-06-26 | 2019-01-01 | 浙江大学 | It is a kind of chiral together with two silicon substrate alkane compounds and its synthetic method and application |
| CN109574946A (en) * | 2018-12-11 | 2019-04-05 | 温州大学 | Diphenylamines-amine-oxazoline ligand, synthetic method and its metal complex and purposes |
| WO2022156320A1 (en) * | 2021-01-22 | 2022-07-28 | 浙江大学 | Method for preparing chiral alkyl compounds by asymmetric hydrogenation reaction of iron complex catalysts catalysing olefins |
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| CN106565764A (en) * | 2016-10-31 | 2017-04-19 | 浙江大学 | Method for synthesizing alpha-chiral silane compound through one-pot method |
| CN106565764B (en) * | 2016-10-31 | 2019-03-22 | 浙江大学 | A kind of method of one pot process alpha-chiral silane compound |
| CN107235995A (en) * | 2017-06-09 | 2017-10-10 | 浙江大学 | A kind of chiral two silane compound and its synthetic method and application |
| CN107235995B (en) * | 2017-06-09 | 2019-12-24 | 浙江大学 | Chiral dihydrosilane compound and synthesis method and application thereof |
| CN108440591A (en) * | 2018-03-20 | 2018-08-24 | 浙江大学 | A kind of synthetic method of chiral two silane compound |
| CN108440591B (en) * | 2018-03-20 | 2021-03-05 | 浙江大学 | Synthesis method of chiral dihydrosilane compound |
| CN109111333A (en) * | 2018-06-26 | 2019-01-01 | 浙江大学 | It is a kind of chiral together with two silicon substrate alkane compounds and its synthetic method and application |
| CN109574946A (en) * | 2018-12-11 | 2019-04-05 | 温州大学 | Diphenylamines-amine-oxazoline ligand, synthetic method and its metal complex and purposes |
| CN109574946B (en) * | 2018-12-11 | 2022-10-04 | 温州大学 | Diphenylamine-amine-oxazoline ligand, synthetic method, metal complex and application thereof |
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