CN102070509A - Method for preparing 3-allyl-3-hydroxy oxindole - Google Patents
Method for preparing 3-allyl-3-hydroxy oxindole Download PDFInfo
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- CN102070509A CN102070509A CN 201110024744 CN201110024744A CN102070509A CN 102070509 A CN102070509 A CN 102070509A CN 201110024744 CN201110024744 CN 201110024744 CN 201110024744 A CN201110024744 A CN 201110024744A CN 102070509 A CN102070509 A CN 102070509A
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- acid
- metal
- otf
- isatin
- clo
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- 0 *[C@@](c(c(N1)c2)c(Cc3ccccc3)cc2Br)(C1=O)O Chemical compound *[C@@](c(c(N1)c2)c(Cc3ccccc3)cc2Br)(C1=O)O 0.000 description 3
- CTEHRYDSOOWVDR-UHFFFAOYSA-N CC(C(c1c(C)c(C)cc(C)c1)=O)=O Chemical compound CC(C(c1c(C)c(C)cc(C)c1)=O)=O CTEHRYDSOOWVDR-UHFFFAOYSA-N 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Cc1ccc(C)cc1 Chemical compound Cc1ccc(C)cc1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- CWGHVZPVKMOHGM-UHFFFAOYSA-N NCC(c1ccccc1N1)(C1=O)O Chemical compound NCC(c1ccccc1N1)(C1=O)O CWGHVZPVKMOHGM-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for preparing 3-allyl-3-hydroxy oxindole, which comprises the following steps of: adding a catalyst, solvent, isatin and silicane in a reaction bulb, stirring at the specific temperature, performing thin layer chromatography (TLC) detection until the isatin disappears, adding ethyl acetate for diluting, dripping concentrated hydrochloric acid, stirring continuously at the room temperature for half an hour, washing once sequentially by using solution of saturated sodium hydrogen carbonate and saturated saline solution, drying an organic phase by using anhydrous magnesium sulfate, and performing column chromatographic separation to obtain the 3-allyl-3-hydroxy oxindole. Various reagents used in the method can be obtained commercially, and have wide sources of raw materials and low cost; the used catalyst has a good catalytic effect and helps to reduce cost and also helps to simplify a process, reduce cost, facilitate aftertreatment process and reduce pollution to the environment.
Description
Technical field
The invention belongs to organic compound process application technical field, be specifically related to a class, prepare the method for 3-allyl group-3-hydroxyl oxidize indoles from isatin and allyl silicane.
Background technology
3-allyl group-3-hydroxyl oxidize indoles
ABe the important pharmaceutical-chemical intermediate of a class, have very high using value.Set out by the synthetic building block of this class, can synthesize some easily and have strong bioactive natural product and drug molecule (formula as follows), as
ConvolutamydineA, B or E,
3-Hydroglucoisatisin,
Donaxaridine, CPC-1,
Flutraminol,
DioxibrassinineDeng.
At present, 3-allyl group-3-hydroxyl oxidize indoles can synthesize by the following method:
1) Barbier of the isatin of indium participation and allyl bromide 98 reacts: this reaction needs to use normal indium powder, and reaction substrate is only limited to no any substituent isatin, and reacts requirement and add 1.5 times of normal sodium iodides.(V.?Nair,?C.?N.?Yayan?and?S. Ros,?
Tetrahedron.,?2001,?57,?9453)。
2) the catalytic allyl group addition reaction to isatin of transition metal palladium: this reaction needs to use expensive palladium (II) as catalyzer, and the catalytic amount requirement is 5 mol%; Need to add three normal boron triethyls; Reaction requires high, needs strict anhydrous and oxygen-free, complicated operation; And reaction substrate is only limited to protected and does not contain the isatin of halogen group, the substrate narrow range.(X.-C.?Qiao,?S.-F.?Zhu?and?Q.-L.?Zhou,?
Tetrahedron:?Asymmetry.,?2009,20,?1254)。
3) the catalytic allyl group addition reaction to isatin of transition metal iridium: this reaction uses the metal iridium complex of 2.5 mol% as catalyzer; Reaction conditions needs strict anhydrous and oxygen-free, and temperature is 60-100
oC; Need to add Virahol, cesium carbonate and 3-nitro-additives such as 4-cyano group phenylcarbinol, complicated operation; Substrate is limited to protected isatin.(J.?Itoh,?S.-B?Han?and?M.?J.?Krische,?
Angew.?Chem.?Int.?Ed.,2009,48,?6313)。
4) the acid catalyzed allyl group tin reagent of Lewis is to the isatin addition reaction: this reaction needs to use 5 mol% trifluoromethanesulfonic acid indiums (III) or trifluoromethanesulfonic acid scandium (III) as catalyzer; Use three equivalent severe toxicity and expensive allyl group tin reagent; Be reflected at anhydrous and oxygen-free ,-20
oCarry out under the C; Substrate has only the 5-bromoisatin of a methyl protection.(V.?Hanhan,?A.?H.?Sahin,?T.?W.?Chang,?J.?C.?Fettinger?and?A.?K.?Franz,?
Angew.?Chem.?Int.?Ed.,2010,?
49,?744)。
5) Claisen of 2-allyl oxidation indoles resets preparation: this reacts, and not only raw material is rare, and productive rate is lower, and by product is more; Resetting needs to use normal organic bases; Reaction conditions is harsh, and temperature needs not wait at room temperature to 110 degree; The substrate narrow range.(T.?Kawasaki,?M.?Nagaoka,?T.?Satoh,?A.?Okamoto,?R.?Ukon?and?A.?Ogawa,?
Tetrahedron.,?2004,?
60,?3493)。
6) isatin and the addition reaction of allyl group grignard reagent preparation: this reaction needs to use and is equivalent to six times of normal allyl grignard reagent of substrate, the strict anhydrous and oxygen-free of operational requirement, and to the functional group such as the nitro of Grignard reagent sensitivity, ester group etc. can not be compatible, the substrate narrow range.(H.-X.?Wu,?F.?Xue,?X.?Xiao?and?Y.?Qin,?
J.?Am.?Chem.?Soc.,?
2010,?
132,?14052)。
In sum, although 3-allyl group-3-hydroxyl oxidize indoles
AAs the important intermediate with extensive use, but existing synthetic method not only requires operation strict, and raw material sources are difficult for, and production cost is higher, and the substrate narrow application range, makes large-scale production face many difficult problems.
Summary of the invention
One of purpose of the present invention is to provide a kind of simple and practical method, can prepare high purity 3-allyl group-3-hydroxyl oxidize indoles from the isatin and the allyl group silica reagent of cheapness.
The object of the present invention is achieved like this:
A kind of method for preparing 3-allyl group-3-hydroxyl oxidize indoles, the concrete steps of this method are:
In reaction flask, add catalyzer M successively
mX
n(y mol%), solvent, isatin (1.0 eq) and silane (z eq) stir under the assigned temperature in-78 ℃ to 100 ℃, TLC detects to the isatin disappearance, add the ethyl acetate dilution, splash into concentrated hydrochloric acid, after continuing under the room temperature to stir half an hour, successively once with the saturated sodium bicarbonate solution washing, the saturated common salt water washing once, the organic phase anhydrous magnesium sulfate drying, column chromatography for separation gets target product.
Described isatin can commercial gained, also can the convenient preparation of reference literature method.[1)
Organic Synthesis,
1925,
5, 71; 2)
Organic Synthesis,
1941,
1, 327; 3) S. J. Garden, J. C. Torres, A. Ferreira, R. B. Silva and A. C. Pinto,
Tetrahedron Lett.,
1997,
38, 1501]; R can be hydrogen, alkyl or aryl in the isatin; R
11, R
12, R
13, R
14Can be substituted radicals such as hydrogen, alkyl, aryl, halogen or heteroatoms.
In the described silane, R
2, R
3, R
4, R
5, R
6, R
7, R
8Can be hydrogen or halogen atom, alkyl, alkoxyl group or aryl etc.
Described solvent can be water or common organic solvent, and as toluene, benzene, methylene dichloride, ether, tetrahydrofuran (THF), acetone, methyl alcohol or the like, its consumption is that the corresponding use range of every mmole isatin is 0.1 mL to 10 mL.
The consumption of ethyl acetate is that every mmole isatin uses the 50-100 milliliter, and the consumption of concentrated hydrochloric acid is that every mmole isatin uses 15-30 to drip (20 about 1 milliliter).
Described catalyzer M
mX
nCan be Lewis acid or
Acid, these acid can be chiralitys, and is also achiral; Catalyst consumption is y mol%, and y is the numerical value between the 0.01-50.
Work as M
mX
nBe
During acid, M is H
+(its valence state is+1), X is corresponding acid radical anion, as Cl
-, NO
3 -, Br
-, SO
4 2-, PO
4 3-Or the like, the concrete numerical value of m and n is-1 ,-2 according to the valence state Z(Z of acid radical anion X ,-3 numerical value such as grade) decision, satisfy * n=0 of (1) * m+(Z).M
mX
nCan be common mineral acid example hydrochloric acid, sulfuric acid, phosphoric acid, perchloric acid or nitric acid, also can be common organic acid such as trifluoracetic acid, p-methyl benzenesulfonic acid, trifluoromethanesulfonic acid or the like; Involved
The structure of acid is as follows:
Work as M
mX
nWhen being Lewis acid, M
mX
nIn metal M can be for example Cs etc. of basic metal, can be for example Mg etc. of alkaline-earth metal, can be for example Sc of transition metal, Cr, Fe, Ni, Ag, Au, Cu, Zn, Hg etc. can be for example Al of earth metals, In, Bi etc., acid ion X
-Can be Cl
-, Br
-Deng the acid ion of oxygen-free acid, also can be OTf
-, ClO
-Acid ion Deng oxygen acid.The concrete numerical value of m and n is+1 ,+2 according to the valence state Y(Y of metallic cation ,+3 numerical value such as grade) and the valence state Z(Z of acid radical anion X be-1 ,-2 ,-3 numerical value such as grade) decision, satisfy * n=0 of (Y) * m+(Z); M
mX
nCan be common metal trifluoroacetate mesylate and hydrate such as Hg (OTf)
2, Cu (OTf)
2, Zn (OTf)
2, In (OTf)
3, Ni (OTf)
2, Cr (OTf)
3, Bi (OTf)
3, Er (OTf)
3, Sc (OTf)
3And Yb (OTf)
3Or the like; Metal perchlorate and hydrate thereof such as In (ClO
4)
38H
2O, Cr (ClO
4)
36H
2O, Al (ClO
4)
39H
2O, Mg (ClO
4)
26H
2O, Fe (ClO
4)
3XH
2O, Cu (ClO
4)
26H
2O, Hg (ClO
4)
23H
2O or the like; Metal tetrafluoroborate and hydrate thereof such as Cu (BF
4)
26H
2O, Hg (BF
4)
23H
2O and Co (BF
4)
26H
2O or the like; Can also be metal fluoride such as AgF, CuF, CuF
2, Hg
2F
2, HgF
2Or the like; Metal chloride such as InCl
3, FeCl
3, HgCl
2And CuCl
2Or the like; Metal bromide such as InBr
3, FeBr
3, HgBr
2And CuBr
2Or the like; Metal nitrate, metal phosphate and metal sulfate or the like, but be not limited to these acid.
Involved in the present invention to catalyzer can be chirality, can be used to prepare the 3-allyl group-3-hydroxyl oxidize indoles of chirality like this.The catalyzer of chirality can be
Acid also can be chiral ligand and the above-mentioned sour chirality Lewis acid catalyst that forms of Lewis.
Chirality involved in the present invention
Acid can be stronger organic acids such as chiral carboxylic acids or chirality phosphonic acids or D-camphorsulfonic acid, chirality sulfonic acid, also can be chirality phenolic compound, chirality thiocarbamide or carbamide compounds, can also be chiral alcohol hydrogen-bond donor catalyzer.Every including in the above-mentioned signal formula
Any one chirality in the acid structural unit
Acid is all in this patent protection domain.
The chirality Lewis acid catalyst that forms by above-mentioned Lewis acid and chiral ligand that arrives involved in the present invention.And chiral ligand can be to have central chirality, the chiral ligand that contains at least one P atom composition of axle chirality or planar chiral, or the chiral ligand of at least one O or N atom composition.Following formula provides some common chiral ligand examples, but is not limited to these parts.
Wherein: R
1, R
2, R
3, R
4, R
5, R
6, R
7Alkyl can be, also aryl can be, can Cheng Huan between them, also Cheng Huan not; Ar is various possible aryl; X is various possible linking groups.
The invention has the beneficial effects as follows:
1. used all ingredients all can commercial gained, and raw material sources are extensive, and are cheap, and can stable existence under all ingredients normal temperature and pressure, and manipulation is convenient, need not special processing.
2, catalyzer is stable to empty G﹠W, and reaction is fit to mass production.
3. operational condition is very gentle, need not the strict operation of anhydrous and oxygen-free, and insensitive to impurity such as moisture, oxygen, reaction process does not relate to very exothermic etc., and is simple to equipment requirements.Aftertreatment also has no special requirements.
4. the cheap catalyst of Shi Yonging when keeping good catalytic effect, reducing cost, has reached simplification technology, has reduced cost, made things convenient for postprocessing working procedures, and the recycling of solvent is convenient, reduces requirements such as environmental pollution.
Embodiment
Below exemplifying embodiment the present invention will better be described, but what need to emphasize is that the present invention never only limits to the represented content of these several exemplifying embodiments.
Following examples have shown not ipsilateral of the present invention.Given data comprise concrete operations and reaction conditions and product, and product purity is identified by nuclear-magnetism.
Embodiment 1
3-allyl group-3-hydroxyl oxidize indoles
1Synthetic:
In 10.0 mL reaction flasks, add three perchloric acid hydrate mercury (II) [Hg (ClO successively
4)
23H
2O, 1.8 mg, 0.004 mmol], isatin
I-1(58.8 mg, 0.40 mmol), anhydrous methylene chloride (2.0 mL), allyl trimethyl silane
II(127.0
μL, 0.80 mmol), stir under the room temperature, it is intact that TLC detects the raw material primitive reaction, and stopped reaction, reaction solution are transferred in the 100 mL round-bottomed flasks, with the dilution of 30 mL ethyl acetate, splash into 10 concentrated hydrochloric acids, continue to stir 5-10 minute, after TLC point plate finds to have only a product point, organic phase is washed once with saturated sodium bicarbonate solution, and the saturated common salt water washing once is spin-dried for the back column chromatography, eluent is (acetone/methylene dichloride=1/10), gets product
1Be white solid 71.8 mg, productive rate 95%.
1H?NMR?(400?MHz,?DMSO-
d 6):?10.21?(s,?1H),?7.27-7.25?(m,?1H),?7.20-7.17?(m,?1H),?6.97-6.94?(m,?1H),?6.80-6.78?(m,?1H),?5.97?(s,?1H),?5.50-5.40?(m,?1H),?4.96-4.92?(m,?2H),?2.63-2.58?(m,?1H),?2.50-2.42?(m,?1H);?
13C?NMR?(100?MHz,?DMSO-
d 6):?178.77,?141.61,?131.77,?131.51,?128.87,?124.15,?121.46,?118.83,?109.46,?75.28,?42.11。
Embodiment 2
3-allyl group-3-hydroxyl-5-oxychlorination indoles
2Synthetic:
In 10.0 mL reaction flasks, add trifluoromethanesulfonic acid mercury (II) [Hg (OTf) successively
2, 2.0 mg, 0.004 mmol], the 5-chlorisatide
I-2(71.2 mg, 0.40 mmol), anhydrous tetrahydro furan (3.0 mL), allyl trimethyl silane
II(127.0
μL, 0.80 mmol), 0 ℃ is stirred down, it is intact that TLC detects the raw material primitive reaction, and stopped reaction, reaction solution are transferred in the 100 mL round-bottomed flasks, with the dilution of 20 mL ethyl acetate, splash into 10 concentrated hydrochloric acids, continue to stir 5-10 minute, after TLC point plate finds to have only a product point, organic phase is washed once with saturated sodium bicarbonate solution, and the saturated common salt water washing once is spin-dried for the back column chromatography, eluent is (acetone/methylene dichloride=1/10), gets product
2Be white solid 85.6 mg, productive rate 97%.
1H?NMR?(400?MHz,?DMSO-
d 6):?d?10.38?(s,?1H),?7.29?(s,?1H),?7.25-7.23?(m,?1H)?6.81-6.79?(m,?1H),?6.16?(s,?1H),?5.49-5.39?(m,?1H),?4.98-4.94?(m,?2H),?2.65-2.60?(m,?1H),?2.50-2.42?(m,?1H);?
13C?NMR?(100?MHz,?DMSO-
d 6):?d?178.42,?140.51,?133.59,?131.38,?128.73,?125.60,?124.31,?119.26,?110.98,?75.47,?41.84;?MS?(EI):?223?(M
+,?7),?182?(100),?41?(35),?184?(30),?43?(23),?63?(19),?126?(17),?57?(17);?HRMS?(EI):?Exact?mass?calcd?for?C
11H
10 35ClNO
2?[M]
+:?223.0400,?Found:?223.0405。
Embodiment 3
3-allyl group-3-hydroxyl-5-nitro Oxoindole
3Synthetic:
In 10.0 mL reaction flasks, add eight perchloric acid hydrate indium (III) [In (ClO successively
4)
38H
2O, 22.0 mg, 0.04 mmol], 5-nitro isatin
I-3(76.9 mg, 0.40 mmol), anhydrous chloroform (3.0 mL), allyl trimethyl silane
II(127.0
μL, 0.80 mmol), 40 ℃ of stirrings, it is intact that TLC detects the raw material primitive reaction, and stopped reaction, reaction solution are transferred in the 100 mL round-bottomed flasks, with the dilution of 30 mL ethyl acetate, splash into 8 concentrated hydrochloric acids, continue to stir 5-10 minute, after TLC point plate finds to have only a product point, organic phase is washed once with saturated sodium bicarbonate solution, and the saturated common salt water washing once is spin-dried for the back column chromatography, eluent is (acetone/methylene dichloride=1/10), gets product
3Be white solid 89.0 mg, productive rate 95%.
1H?NMR?(400?MHz,?DMSO-
d 6):?d?10.99?(s,?1H),?8.20-8.18?(m,?1H),?8.12?(s,?1H),?7.00-6.98?(m,?1H),?6.36?(s,?1H),?5.53-5.43?(m,?1H),?4.99-4.96?(m,?2H),?2.74-2.69?(m,?1H),?2.52-2.47?(m,?1H);?
13C?NMR?(100?MHz,?DMSO-
d 6):?d?178.98,?148.14,?142.12,?132.44,?130.94,?126.28,?119.72,?119.70,?109.75,?75.06,?41.56;?MS?(EI):?234?(M
+,?7),?193?(100),?41?(66),?43?(50),?147?(50),?55?(35),?57?(34),?91?(27);?HRMS?(EI):?Exact?mass?calcd?for?C
11H
10N
2O
4?[M]
+:?234.0641,?Found:?234.0642。
Embodiment 4
3-allyl group-3-hydroxyl-6-bromine Oxoindole
4Synthetic:
In 10.0 mL reaction flasks, add catalyzer trifluoromethanesulfonic acid indium (III) [In (OTf) successively
3, 24.0 mg, 0.04 mmol], the 6-bromo-isatin
I-4(90.9 mg, 0.40 mmol), anhydrous tetracol phenixin (3.0 mL), allyl trimethyl silane
II(127.0
μL, 0.80 mmol), be stirred under 50 ℃ the raw material primitive reaction intact after, reaction solution is transferred in the 100 mL round-bottomed flasks, with the dilution of 30 mL ethyl acetate, splash into 8 concentrated hydrochloric acids, continue to stir 5-10 minute, after TLC point plate finds to have only a product point, organic phase is washed once with saturated sodium bicarbonate solution, and the saturated common salt water washing once is spin-dried for the back column chromatography, eluent is (acetone/methylene dichloride=1/10), gets product
4Be white solid 88.9 mg, productive rate 95%.
1H?NMR?(400?MHz,?DMSO-
d 6):?d?10.39?(s,?1H),?7.22-7.13?(m,?2H),?6.94?(m,?1H),?6.11?(s,?1H),?5.48-5.38?(m,?1H),?4.96-4.93?(m,?2H),?2.62-2.57?(m,?1H),?2.46-2.41?(m,?1H);?
13C?NMR?(100?MHz,?DMSO-
d 6):?d?178.58,?143.33,?131.40,?130.82,?126.06,?124.14,?121.50,?119.25,?112.36,?75.07,?41.82。
Embodiment 5
3-allyl group-3-hydroxyl-7-oxychlorination indoles
5Synthetic:
In 10.0 mL reaction flasks, add perchloric acid [HClO successively
4, 0.6 mg, 0.004 mmol, aq. 72%], the 7-chlorisatide
I-5(72.5mg, 0.40 mmol), anhydrous diethyl ether (2.0 mL), allyl trimethyl silane
II(127.0
μL, 0.80 mmol), 30 ℃ are stirred down, it is intact that TLC detects the raw material primitive reaction, and stopped reaction, reaction solution are transferred in the 100 mL round-bottomed flasks, with the dilution of 30 mL ethyl acetate, splash into 8 concentrated hydrochloric acids, continue to stir 5-10 minute, after TLC point plate finds to have only a product point, organic phase is washed once with saturated sodium bicarbonate solution, and the saturated common salt water washing once is spin-dried for the back column chromatography, eluent is (acetone/methylene dichloride=1/10), gets product
5Be white solid 74.2 mg, productive rate 83%.
1H?NMR?(400?MHz,?CDCl
3):?d?8.37?(s,?1H),?7.26-7.24?(m,?2H),?7.04-7.00?(m,?1H),?5.69-5.59?(m,?1H),?5.13-5.09?(m,?2H),?3.80?(s,?br,?1H),?2.77-2.72?(m,?1H),?2.64-2.59?(m,?1H);?
13C?NMR?(100?MHz,?CDCl
3):?d?179.14,?137.92,?131.54,?129.81,?129.52,?123.93,?122.74,?120.92,?115.47,?77.14,?42.77;?MS?(EI):?223?(M
+,?6),?224?[(M+H)
+,?1],?182?(100),?41?(30),?184?(30),?90?(27),?43?(22),?63?(19);?HRMS?(EI):?Exact?mass?calcd?for?C
11H
10 35ClNO
2?[M]
+:?223.0400,?Found:?223.0402。
Embodiment 6
3-allyl group-3-hydroxyl-5,7-dimethyl oxidation indoles
6Synthetic:
In 10.0 mL reaction flasks, add successively p-methyl benzenesulfonic acid [
p-Me-PhSO
3H, 0.7 mg, 0.004 mmol], 5,7-dimethyl isatin
I-6(71.2 mg, 0.40 mmol), dry toluene (2.0 mL), allyl trimethyl silane
II(127.0
μL, 0.80 mmol), be stirred under 100 ℃ the raw material primitive reaction intact after, stopped reaction, reaction solution is transferred in the 100 mL round-bottomed flasks, with the dilution of 25 mL ethyl acetate, splashes into 8 concentrated hydrochloric acids, continue to stir after 5-10 minute, organic phase is washed once with saturated sodium bicarbonate solution, and the saturated common salt water washing once is spin-dried for the back column chromatography, eluent is (acetone/methylene dichloride=1/10), gets product
6Be white solid 86.3 mg, productive rate 97%.
1H?NMR?(400?MHz,?DMSO-
d 6):?d?10.18?(s,?1H),?6.90?(s,?1H),?6.81?(s,?1H),?5.89?(s,?1H),?5.47-5.37?(m,?1H),?4.96-4.92?(m,?2H),?2.59-2.41?(m,?2H),?2.21?(s,?3H),?2.13?(s,?3H);?
13C?NMR?(100?MHz,?DMSO-
d 6):?d?179.21,?137.64,?131.96,?131.30,?130.51,?130.18,?122.07,?118.65,?118.33,?75.51,?42.19,?20.62,?16.20;?MS?(EI):?217?(M
+,?5),?218?[(M+H)
+,?1],?176?(100),?41?(40),?77?(20),?91?(18),?118?(12),?177?(11);?HRMS?(EI):?Exact?mass?calcd?for?C
13H
15NO
2?[M]
+:?217.1103,?Found:?217.1104。
Embodiment 7
3-allyl group-3-hydroxyl-5,7-dibromo Oxoindole
7Synthetic:
In 10.0 mL reaction flasks, add three hydration Tetrafluoroboric acid mercury (II) [Hg (BF successively
4)
23H
2O, 1.7 mg, 0.004 mmol], 5,7-two bromo-isatins
I-7(121.8 mg, 0.40 mmol), anhydrous methanol (2.0 mL), allyl trimethyl silane
II(127.0
μL, 0.80 mmol), be stirred under the room temperature raw material primitive reaction intact after, stopped reaction, reaction solution are transferred in the 100 mL round-bottomed flasks, dilute with 25 mL ethyl acetate, splash into 10 concentrated hydrochloric acids, continue to stir 5-10 minute, after TLC point plate found to have only a product point, organic phase with the saturated sodium bicarbonate solution washing once, the saturated common salt water washing once, be spin-dried for the back column chromatography, eluent is (acetone/methylene dichloride=1/10), gets product
7Be white solid 136.5 mg, productive rate 98%.
1H?NMR?(400?MHz,?DMSO-
d 6):?d?10.74?(s,?1H),?7.58?(s,?1H),?7.43?(s,?1H),?6.30?(s,?1H),?5.46-5.38?(m,?1H),?4.98-4.94?(m,?2H),?2.65-2.60?(m,?1H)，2.50-2.45?(m,?1H);?
13C?NMR?(100?MHz,?DMSO-
d 6):?d?178.14,?140.62,?135.26,?133.47,?130.99,?126.25,?119.67,?113.80,?102.84,?76.36,?41.85;?MS?(EI):?345?(M
+,?4),?306?(100),?304?(52),?41?(50),?308?(49),?91?(44),?66?(32),?63?(25);?HRMS?(EI):?Exact?mass?calcd?for?C
11H
9 79Br
2NO
2?[M]
+:?344.9000,?Found:?344.8999。
Embodiment 8
3-allyl group-3-hydroxyl-4,6-dibromo Oxoindole
8Synthetic:
In 10.0 mL reaction flasks, add Salzburg vitriol (II) [CuSO successively
45H
2O, 10.0 mg, 0.04 mmol], 4,6-two bromo-isatins
I-8(123.0 mg, 0.40 mmol), dry-out benzene (2.0 mL), allyl trimethyl silane
II(127.0
μL, 0.80 mmol), be stirred under 70 ℃ the raw material primitive reaction intact after, stopped reaction, reaction solution is transferred in the 100 mL round-bottomed flasks, with the dilution of 20 mL ethyl acetate, splashes into 6 concentrated hydrochloric acids, continue to stir after 5-10 minute, organic phase is washed once with saturated solution, and the saturated common salt water washing once is spin-dried for the back column chromatography, eluent is (acetone/methylene dichloride=1/10), gets product
8Be white solid 131.2 mg, productive rate 94%.
1H?NMR?(400?MHz,?DMSO-
d 6):?d?10.62?(s,?1H),?7.34?(s,?1H),?6.92?(s,?1H),?6.20?(s,?1H),?5.26-5.16?(m,?1H),?4.99-4.88?(m,?2H),?3.04-3.00?(m,?1H),?2.57-2.50?(m,?1H);
?13C?NMR?(100?MHz,?DMSO-
d 6):?d?177.73,?145.29,?130.58,?128.23,?127.14,?122.35,?119.67,?119.43,?111.84,?76.90,?38.80。
Embodiment 9
3-allyl group-3-hydroxy-5-methyl base Oxoindole
9Synthetic:
In 10.0 mL reaction flasks, add ferric bromide (III) [FeBr successively
3, 24.0 mg, 0.08 mmol], 5-methyl isatin
I-9(102.9 mg, 0.40 mmol), anhydrous tetrahydro furan (2.0 mL), allyl trimethyl silane
II(127.0
μL, 0.80 mmol) ,-78 ℃ are stirred down, it is intact that TLC detects the raw material primitive reaction, and stopped reaction, reaction solution are transferred in the 100 mL round-bottomed flasks, with the dilution of 25 mL ethyl acetate, splash into 10 concentrated hydrochloric acids, continue to stir 5-10 minute, after TLC point plate finds to have only a product point, organic phase is washed once with saturated sodium bicarbonate solution, and the saturated common salt water washing once is spin-dried for the back column chromatography, eluent is (acetone/methylene dichloride=1/10), gets product
9Be white solid 115.9 mg, productive rate 97%.
1H?NMR?(400?MHz,?CDCl
3):?d?7.21-7.14?(m,?6H),?6.90-6.88?(m,?1H),?6.49-6.47?(m,?1H),?5.55-5.44?(m,?1H),?5.07-4.96?(m,?2H),?4.94?(ABd,?
J?=?16.0?Hz,?1H),?4.58?(ABd,?
J?=?16.0?Hz,?1H),?3.88?(s,?br,?1H),?2.77-2.72?(m,?1H),?2.68-2.62?(m,?1H),?2.21?(s,?3H);?
13C?NMR?(100?MHz,?CDCl
3):?d?178.01,?139.92,?135.45,?132.66,?130.63,?129.68,?128.63,?127.52,?127.21,?124.85,?120.29,?109.16,?76.10,?43.75,?42.92,?20.99。
Embodiment 10
3-allyl group-3-hydroxyl-5-fluorine Oxoindole
10Synthetic:
In 10.0 mL reaction flasks, add Indium-111 chloride (III) [InCl successively
3, 27.9 mg, 0.12 mmol], the 5-fluoro indigo red
I-10(102.5 mg, 0.40 mmol), anhydrous tetrahydro furan (2.0 mL), allyl trimethyl silane
II(127.0
μL, 0.80 mmol) ,-40 ℃ are stirred down, it is intact that TLC detects the raw material primitive reaction, and stopped reaction, reaction solution are transferred in the 100 mL round-bottomed flasks, with the dilution of 30 mL ethyl acetate, splash into 9 concentrated hydrochloric acids, continue to stir 5-10 minute, after TLC point plate finds to have only a product point, organic phase is washed once with saturated sodium bicarbonate solution, and the saturated common salt water washing once is spin-dried for the back column chromatography, eluent is (acetone/methylene dichloride=1/10), gets product
10Be white solid 114.8 mg, productive rate 96%.
1H?NMR?(400?MHz,?CDCl
3):?d?7.31-7.25?(m,?5H),?7.16-7.14?(m,?1H),?6.88-6.84?(m,?1H),?6.60-6.56?(m,?1H),?5.61-5.51?(m,?1H),?5.14-5.08?(m,?2H),?4.99?(ABd,?
J?=?16.0?Hz,?1H),?4.66?(ABd,?
J?=?16.0?Hz,?1H),?4.60?(s,?br,?1H),?2.86-2.81?(m,?1H),?2.75-2.70?(m,?1H);?
13C?NMR?(100?MHz,?CDCl
3):?d?178.15,?160.59,?158.18,?138.07,?134.99,?131.56,?131.49,?130.09,?128.73,?127.70,?127.17,?120.66,?115.71,?115.48,?112.47,?112.22,?110.11,?110.03,?76.32,?43.89,?42.82;?
19F?NMR?(376?MHz,?CDCl
3):?d?-119.46;?MS?(EI):?297?(M
+,?3),?298?[(M+1)
+,?1],?91?(100),?41?(44),?43?(32),?57?(22),?55?(16),?69?(15);?HRMS?(EI):?Exact?mass?calcd?for?C
18H
16FNO
2?[M]
+:?297.1165,?Found:?297.1170。
Embodiment 11
3-allyl group-3-hydroxy-5-methyl oxygen base Oxoindole
11Synthetic:
In 10.0 mL reaction flasks, add indium tribromide (III) [InBr successively
3, 42 mg, 0.12 mmol], 5-methoxyl group isatin
I-11(76.8 mg, 0.40 mmol), anhydrous tetrahydro furan (3.0 mL), allyl trimethyl silane
II(127.0
μL, 0.80 mmol) ,-20 ℃ are stirred down, it is intact that TLC detects the raw material primitive reaction, and stopped reaction, reaction solution are transferred in the 100 mL round-bottomed flasks, with the dilution of 30 mL ethyl acetate, splash into 10 concentrated hydrochloric acids, continue to stir 5-10 minute, after TLC point plate finds to have only a product point, organic phase is washed once with saturated sodium bicarbonate solution, and the saturated common salt water washing once is spin-dried for the back column chromatography, eluent is (acetone/methylene dichloride=1/10), gets product
11Be white solid 92.8 mg, productive rate 99%.
1H?NMR?(400?MHz,?CDCl
3):?d?7.01?(s,?1H),?6.84-6.82?(m,?1H),?6.73-6.71?(m,?1H),?5.66-5.56?(m,?1H),?5.11-5.05?(m,?2H),?3.79?(s,?3H),?3.71?(s,?br,?1H),?3.14?(s,?3H),?2.76-2.71?(m,?1H),?2.63-2.57?(m,?1H);
?13C?NMR?(100?MHz,?CDCl
3):?d?177.60,?156.30,?136.56,?130.98,?130.48,?120.25,?114.08,?111.27,?108.76,?76.24,?55.82,?42.91,?26.18。
Embodiment 12
(
S)-3-allyl group-3-hydroxyl oxidize indoles
1Synthetic:
In 10.0 mL reaction flasks, add three perchloric acid hydrate mercury (II) [Hg (ClO successively
4)
23H
2O, 3.6 mg, 0.008 mmol], (
S)-1,1'-dinaphthalene-2, the two diphenylphosphines of 2'-[(
S)-BINAP, 5.0 mg, 0.008 mmol], anhydrous tetrahydro furan (3.0 mL) stirs 2 h under the room temperature, add isatin
I-1(58.8 mg, 0.40 mmol), place-40 ℃ down stir 0.5 h after, add allyl trimethyl silane
II(127.0
μL, 0.80 mmol), it is intact that TLC detects the raw material primitive reaction, stopped reaction, reaction solution are transferred in the 100 mL round-bottomed flasks, dilute with 30 mL ethyl acetate, splash into 6 concentrated hydrochloric acids, at room temperature continue to stir 5-10 minute, after TLC point plate found to have only a product point, organic phase with the saturated sodium bicarbonate washing once, the saturated common salt water washing once, be spin-dried for the back column chromatography, eluent be (acetone/methylene dichloride=1/10), must product (
S)-
1, productive rate 93%.[α]
D 20?=?-3.2
o?(c?=?1.00,?MeOH);?56%?ee。(Chiracel OD-H post, 90:10 normal hexane: Virahol).In this example (
SProduct among the nucleus magnetic hydrogen spectrum of)-1 and carbon spectrum and mass-spectrometric data and the embodiment 1
1Consistent.
Embodiment 13
(
S)-3-allyl group-3-hydroxyl-4,6-dibromo Oxoindole
8Synthetic:
In 10.0 mL reaction flasks, add three perchloric acid hydrate mercury (II) [Hg (ClO successively
4)
23H
2O, 1.8 mg, 0.004 mmol], (
S)-1, the two diphenylphosphines of 1'-dinaphthalene-2--2'-methoxyl group part [(
S)-MOP, 1.9 mg, 0.004 mmol], anhydrous tetrahydro furan (4.0 mL) stirs 2 h under the room temperature, add 4,6-two bromo-isatins
I-8(122.0 mg, 0.40 mmol), place-40 ℃ down stir 0.5 h after, add allyl trimethyl silane
II(127.0
μL, 0.80 mmol), it is intact that TLC detects the raw material primitive reaction, stopped reaction, reaction solution are transferred in the 100 mL round-bottomed flasks, dilute with 30 mL ethyl acetate, splash into 10 concentrated hydrochloric acids, continue to stir 5-10 minute, after TLC point plate found to have only a product point, organic phase with the saturated sodium bicarbonate washing once, the saturated common salt water washing once, be spin-dried for the back column chromatography, eluent be (acetone/methylene dichloride=1/10), must product (
S)-
8, productive rate 94%.[α]
D 20?=?+7.8
o?(c?=?1.05,?MeOH);?63%?ee。(Chiracel AD-H post, 90:10 normal hexane: Virahol).In this example (
S)-
8Nucleus magnetic hydrogen spectrum and the product among carbon spectrum and mass-spectrometric data and the embodiment 8
8Consistent.
Embodiment 14
(
S)-3-allyl group-3-hydroxyl oxidize indoles
1Synthetic:
In 10.0 mL reaction flasks, add three perchloric acid hydrate mercury (II) [Hg (ClO successively
4)
23H
2O, 3.6 mg, 0.008 mmol], (
S)-I phosphine part [(
S)-I, 3.1 mg, 0.008 mmol], anhydrous tetrahydro furan (3.0 mL) stirs 2 h under the room temperature, add isatin
I-1(58.8 mg, 0.40 mmol), place-40 ℃ down stir 0.5 h after, add allyl trimethyl silane
II(127.0
μL, 0.80 mmol), it is intact that TLC detects the raw material primitive reaction, stopped reaction, reaction solution are transferred in the 100 mL round-bottomed flasks, dilute with 30 mL ethyl acetate, splash into 10 concentrated hydrochloric acids, continue to stir 5-10 minute, after TLC point plate found to have only a product point, organic phase with the saturated sodium bicarbonate washing once, the saturated common salt water washing once, be spin-dried for the back column chromatography, eluent be (acetone/methylene dichloride=1/10), must product (
S)-
1, productive rate 90%.[α]
D 20?=?-3.7
o?(c?=?1.05,?MeOH);?58%?ee。(Chiracel OD-H post, 90:10 normal hexane: Virahol).In this example (
SProduct among the nucleus magnetic hydrogen spectrum of)-1 and carbon spectrum and mass-spectrometric data and the embodiment 1
1Consistent.
Embodiment 15
(
R)-3-allyl group-3-hydroxyl oxidize indoles
1Synthetic:
In 10.0 mL reaction flasks, add three perchloric acid hydrate mercury (II) [Hg (ClO successively
4)
23H
2O, 3.6 mg, 0.008 mmol], (1
R, 2
R)-(+)-1,2-diamines basic ring hexyl-
N,
N'-two (2 '-diphenylphosphine base benzoyl) [(1
R, 2
R)-II, 5.5 mg, 0.008 mmol], anhydrous tetrahydro furan (3.0 mL) stirs 2 h under the room temperature, add isatin
I-1(58.8 mg, 0.40 mmol), place-40 ℃ down stir 0.5 h after, add allyl trimethyl silane
II(127.0
μL, 0.80 mmol), it is intact that TLC detects the raw material primitive reaction, stopped reaction, reaction solution are transferred in the 100 mL round-bottomed flasks, dilute with 30 mL ethyl acetate, splash into 10 concentrated hydrochloric acids, continue to stir 5-10 minute, after TLC point plate found to have only a product point, organic phase with the saturated sodium bicarbonate washing once, the saturated common salt water washing once, be spin-dried for the back column chromatography, eluent be (acetone/methylene dichloride=1/10), must product (
R)-
1, productive rate 81%.[α]
D 20?=?5.1
o?(c?=?1.01,?MeOH);?71%?ee。(Chiracel OD-H post, 90:10 normal hexane: Virahol).In this example (
RProduct among the nucleus magnetic hydrogen spectrum of)-1 and carbon spectrum and mass-spectrometric data and the embodiment 1
1Consistent.
Claims (1)
1. method for preparing 3-allyl group-3-hydroxyl oxidize indoles is characterized in that the concrete steps of this method are:
In reaction flask, add catalyzer M successively
mX
n, solvent, isatin and silane, assigned temperature stirs down, TLC detects to the isatin disappearance, add the ethyl acetate dilution, splash into concentrated hydrochloric acid, after continuing under the room temperature to stir half an hour, successively once with saturated sodium bicarbonate solution, each washing of saturated aqueous common salt, organic phase anhydrous magnesium sulfate drying, column chromatography for separation get 3-allyl group-3-hydroxyl oxidize indoles;
R is hydrogen, alkyl or aryl in the used isatin; R
11, R
12, R
13And R
14Be hydrogen, alkyl, aryl, halogen or hetero atom substituents group;
R in the used silane
2, R
3, R
4, R
5, R
6, R
7And R
8Be hydrogen or halogen atom, alkyl, alkoxyl group or aryl;
Described solvent is water or organic solvent, and organic solvent is toluene, benzene, methylene dichloride, ether, tetrahydrofuran (THF), acetone or methyl alcohol, and its consumption is that the corresponding use range of every mmole isatin is 0.1 mL to 50 mL;
The consumption of described ethyl acetate is that every mmole isatin uses the 50-100 milliliter, and the consumption of concentrated hydrochloric acid is that every mmole isatin uses 15-30 to drip, and 20 is 1 milliliter;
Described assigned temperature is to carry out under the arbitrary temp in-78 ℃ to 100 ℃;
Described catalyzer be Lewis acid or
Acid, these acid are chiralitys or achiral; Catalyst consumption is y mol%, and y is the numerical value between the 0.01-50; Work as M
mX
nBe
During acid, M is H
+, its valence state is+1; X is an acid radical anion, and described acid radical anion is Cl
-, NO
3 -, Br
-, SO
4 2-And PO
4 3-The concrete numerical value of m and n is according to the valence state Z of acid radical anion X decision, and Z be-1 ,-2, and-3, * n=0 of satisfied (1) * m+(Z); M
mX
nBe mineral acid or organic acid; Mineral acid is hydrochloric acid, sulfuric acid, phosphoric acid, perchloric acid and nitric acid; Organic acid is trifluoracetic acid, p-methyl benzenesulfonic acid and trifluoromethanesulfonic acid; Involved
The structure of acid is as follows:
Work as M
mX
nWhen being Lewis acid, M
mX
nIn metal M be basic metal, alkaline-earth metal, transition metal or earth metals; Basic metal is Cs; Alkaline-earth metal is Mg; Transition metal is Sc, Cr, Fe, Ni, Ag, Au, Cu, Zn and Hg; Earth metals is Al, In and Bi; Acid ion X
-Be the acid ion of oxygen-free acid or the acid ion of oxygen acid; The acid ion of oxygen-free acid is Cl
-And Br
-, the acid ion of oxygen acid is OTf
-And ClO
-The concrete numerical value of m and n is according to the valence state Z decision of the valence state Y and the acid radical anion X of metallic cation, and Y is+1 ,+2 ,+3; Z is-1 ,-2 ,-3; Satisfy * n=0 of (Y) * m+(Z); M
mX
nBe metal trifluoroacetate mesylate and hydrate thereof, metal perchlorate and hydrate, metal tetrafluoroborate and hydrate thereof, metal fluoride, metal chloride, metal bromide, metal nitrate, metal phosphate or metal sulfate; Metal trifluoroacetate mesylate and hydrate thereof are Hg (OTf)
2, Cu (OTf)
2, Zn (OTf)
2, In (OTf)
3, Ni (OTf)
2, Cr (OTf)
3, Bi (OTf)
3, Er (OTf)
3, Sc (OTf)
3And Yb (OTf)
3Metal perchlorate and hydrate thereof are In (ClO
4)
38H
2O, Cr (ClO
4)
36H
2O, Al (ClO
4)
39H
2O, Mg (ClO
4)
26H
2O, Fe (ClO
4)
3XH
2O, Cu (ClO
4)
26H
2O and Hg (ClO
4)
23H
2O; Metal tetrafluoroborate and hydrate thereof are Cu (BF
4)
26H
2O, Hg (BF
4)
23H
2O and Co (BF
4)
26H
2O; Metal fluoride is AgF, CuF, CuF
2, Hg
2F
2And HgF
2Metal chloride is InCl
3, FeCl
3, HgCl
2And CuCl
2Metal bromide is InBr
3, FeBr
3, HgBr
2And CuBr
2
Above-mentioned Lewis is sour to form chirality Lewis acid with chiral ligand, and chiral ligand is the chiral ligand that at least one P atom is formed that contains with central chirality, axle chirality or planar chiral, or the chiral ligand of at least one O or N atom composition; Have following structure:
Wherein: R
1, R
2, R
3, R
4, R
5, R
6, R
7Alkyl can be, also aryl can be, can Cheng Huan between them, also Cheng Huan not; Ar is various possible aryl; X is various possible linking groups.
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Cited By (5)
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|---|---|---|---|---|
| CN102659662A (en) * | 2012-03-28 | 2012-09-12 | 华东师范大学 | A synthetic method of 3-R-3-hydroxy-2-oxindole compound |
| CN103864668A (en) * | 2012-12-14 | 2014-06-18 | 华东师范大学 | Preparing method of 3-hydroxyloxoindole derivatives |
| CN103936649A (en) * | 2014-03-29 | 2014-07-23 | 贵州大学 | 3-(2-acrylate)-3-thio oxindole compound and preparation method thereof |
| CN104098501A (en) * | 2014-06-23 | 2014-10-15 | 华东师范大学 | 3-difluoro alkyl substituted all-carbon quaternary carbon oxoindole derivative and synthetic method thereof |
| CN105130873A (en) * | 2015-08-06 | 2015-12-09 | 华东师范大学 | 3-difluoroalkyl substituted amino oxindole derivative and synthesis method thereof |
-
2011
- 2011-01-24 CN CN201110024744A patent/CN102070509B/en not_active Expired - Fee Related
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| 《Angew.Chem.Int.Ed.》 20091222 Nadine V. Hanhan et al. Catalytic Asymmetric Synthesis of Substituted 3-Hydroxy-2-Oxindoles 744-747 1 第49卷, 第4期 2 * |
| 《Angew.Chem.Int.Ed》 20070803 Uwe Schneider et al. Catalytic Activation of Pinacolyl Allylboronate with Indium(I):Development of a General Catalytic Allylboration of Ketones 5909-5912 1 第46卷, 第31期 2 * |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659662A (en) * | 2012-03-28 | 2012-09-12 | 华东师范大学 | A synthetic method of 3-R-3-hydroxy-2-oxindole compound |
| CN103864668A (en) * | 2012-12-14 | 2014-06-18 | 华东师范大学 | Preparing method of 3-hydroxyloxoindole derivatives |
| CN103936649A (en) * | 2014-03-29 | 2014-07-23 | 贵州大学 | 3-(2-acrylate)-3-thio oxindole compound and preparation method thereof |
| CN103936649B (en) * | 2014-03-29 | 2016-05-04 | 贵州大学 | 3-(2-acrylate)-3-sulfo-Oxoindole compound and preparation method thereof |
| CN104098501A (en) * | 2014-06-23 | 2014-10-15 | 华东师范大学 | 3-difluoro alkyl substituted all-carbon quaternary carbon oxoindole derivative and synthetic method thereof |
| CN104098501B (en) * | 2014-06-23 | 2016-07-27 | 华东师范大学 | The substituted full carbon quaternary carbon oxoindole derivative of 3-fluoroalkyl and synthetic method thereof |
| CN105130873A (en) * | 2015-08-06 | 2015-12-09 | 华东师范大学 | 3-difluoroalkyl substituted amino oxindole derivative and synthesis method thereof |
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