CN1331854C - a-methyl-beta,-beta-double indolene compound, synthesis and use thereof - Google Patents
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- CN1331854C CN1331854C CNB2005100236335A CN200510023633A CN1331854C CN 1331854 C CN1331854 C CN 1331854C CN B2005100236335 A CNB2005100236335 A CN B2005100236335A CN 200510023633 A CN200510023633 A CN 200510023633A CN 1331854 C CN1331854 C CN 1331854C
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Abstract
The present invention relates to an alpha-methyl-beta, beta-bisindole alkone compound, a synthetic method and an application thereof. The structural formula of the bisindole alkone compound is disclosed in the right chemical formula, wherein R<1> represents H, C<1-16> alkyl and electron-rich or weak electron withdrawing substituent, n=0 to 4, and R<2> represents C<1-16> alkyl or pentatomic ring or hexatomic ring or non-annular heteroatom substituent. The C<1-16> alkyl is alkyl or aryl, wherein the aryl can be phenyl, naphthyl, phenyl substituted (C<1-4>) alkyl, etc. The electron-rich substituent is methyl, methoxy, benzyloxy, etc. The weak electro withdrawing substituent is halogen. The pentatomic ring or hexatomic ring or non-annular heteroatom substituent is morphia pyrinyl (C<1-4>) alkyl, sulfamide or acyl, etc. The method of the present invention has the advantages of available raw material, simple operation, convenient post processing, higher reaction yield, simple reacting equipment and easy commercial process and is a convenient and effective synthetic method.
Description
Technical field
The present invention relates to a class double-indole ketone compounds, new synthetic method and uses thereof.This method is a catalyzer with Lewis acid, and to 1, the multiple nucleophilic addition of 2-connection ketenes synthesizes Beta-methyl-β, beta-double indolene compound by indoles.This compound is as a kind of important molecule stripping and slicing, itself may have certain physiologically active, also can be used as synthon and further synthesize some compounds that some contain two indoles, these compounds that contain two indoles may all have very strong biological activity, manyly can be used as antibiotic etc and are widely used.
Background technology
The bisindole compound is present in (as parasitic bacteria, the metabolite of tunicates and sponges etc.) in the different natural products, and great majority have the important physical activity.Therefore, this compounds has caused numerous scientists' great interest." (a) Bifulco, G.; Bruno, I.; Riccio, R.; Lavayre, J.; Bourdy, G.J. Nat.Prod.1995,58,1254. (b) Morris, S.A.; Anderson, R.A.Tetrahedron 1990,46,715. (c) Wright, A.E.; Pomponi, S.A.; Cross, S.S.; McCarthy, P.J.Org.Chem.1992,57,4772. (d) Tsujii, S.; Rinehart, K.L.J.Org.Chem.1988,53,5446. " show various pharmacologically active simultaneously to treatment bromyalgia as bisindole Compound I and II, confirmed fatigue and Anaphylaxis enteritis complication have good effect.These compounds can also suppress the regeneration of the breast cancer cell of estrogen-induced simultaneously.III (vibrindole A) is to Staphylococcusaureus, and S.albus and B.subtilis have anti-microbial activity, can be used as the surrogate of gentamicin.IV (Streptindole) be first from bacterium metabolite, separate obtain have genotoxicity and an active bisindole compound of DNA-damaging." (a) Porter, J.K.; Bacon, C.W.; Robbins, J.D.; Himmelsbach, D.S.; Higman, H.C.J.Agric.Food Chem.1977,25,88. (b) T.Osawa and M.Namiki, Tetrahedron Lett.1983,24,4719. (c) Bifulco, G.; Bruno, I.; Riccio, R.; Lavayre, J.; Bourdy, G.J.Nat.Prod.1994,57,1254. (d) Bell, R.; Carmeli, S.; Sar, N.J.Nat.Prod.1994,57,1587. (e) Garbe, T.R.; Kobayashi, M.; Shimizu, N.; Takesue, N.; Ozawa, M.; Yukawa, H.J.Nat.Prod.2000,63,596. " bis (indolyl) pyrazines etc. is inhibited to the cancer cell of many types." (a) Jiang, B.; Gu, X.-H.Bioorg.Med.Chem.2000,53,363. " although document " (a) Chen, D.P.; Yu, L.B.; Wang, P.G.Tetrahedron Lett.1996,37,4467 (b) Xie, W.H.; Bloom.eld, K.M.; Jin, Y.F.; Dolney, N.Y.; Wang, P.G.Synlett1999,4,498. (c) Babu, G.; Sridhar, N.; Perumal, P.T.Synth.Commun.2000,30,1609. (d) Yadav, J.S.; Reddy, B.V.S.; Padmavani, B.; Gupta, M.K.Tetrahedron Lett.2004,45,7577. (e) Mi, X.Luo, S.; He, J.; Cheng, J-P.Tetrahedron Letter.2004,45,4567. (f) Farhanullah; Sharon, A.; Maulik, P.R.; Rama, V.J.Tetrahedron Lett.2004,45,5099. " in reported by the synthetic α of the addition reaction of indoles and aldehyde (or imines) or alkynes, the method for α-bis (indolyl) methane compound.But by 1,2-connection ketenes sets out through the synthetic β of the nucleophilic addition of indoles, and the beta-double indolene compound method was not reported.
-bis(indolyl)pyrazines bis(indolyl)thiazoles bis(indolyl)pyrimidines
Summary of the invention
The purpose of this invention is to provide a kind of new compound, i.e. Beta-methyl-β, beta-double indolene compound.
Another purpose of the present invention provides a kind of effective synthetic method of above-claimed cpd.Utilize indoles to 1, the multiple nucleophilic addition of 2-connection ketenes can highly selective synthesize Beta-methyl-β, beta-double indolene compound.
The purpose of this invention is to provide a kind of above-mentioned β--methyl-β, the purposes of beta-double indolene compound.
Alpha-Methyl-β of the present invention, beta-double indolene compound, its structural formula is:
Wherein, R
1Be H, C
1-16Alkyl, electron rich or feebleness electron withdrawing substituents, n=0～4; R
2Be C
1-16Alkyl, five or six-membered cyclic or acyclic hetero atom substituents; Described C
1-16Alkyl be alkyl or aryl, described aryl can be (the C that phenyl, naphthyl or phenyl replace
1～4) alkyl; Described abundant electron substituents is methyl, methoxyl group or benzyloxy; Described feebleness electron withdrawing substituents is a halogen; Described five or six-membered cyclic or acyclic hetero atom substituents be morphine forest base (C
1～4) alkyl, sulphonamide or acyl group.
The invention provides a kind of synthetic β--methyl-β, the beta-double indolene compound novel method, reaction formula is as follows:
Wherein, R
1And R
2As previously mentioned.
Method of the present invention is in organic solvent, and with indoles or derivatives thereof, 1, ketenes dissolving of 2-connection and Lewis acid (Lewis acid) catalyzer obtain Alpha-Methyl-β, beta-double indolene compound in suitable temperature and suitable time internal reaction.Indoles or derivatives thereof, 1, the mol ratio of 2-connection ketenes and Lewis acid catalyst is 0.2～10: 1: 0.001～10.0.Recommending mol ratio is 2.2～3: 1: 0.001～0.20.
Wherein catalyst system therefor Lewis acid can be trifluoromethanesulfonic acid scandium (Sc (OTf)
3), copper trifluoromethanesulfcomposite (Cu (OTf)
2), trifluoromethanesulfonic acid indium (In (OTf)
3), trifluoromethanesulfonic acid zinc (Zn (OTf)
2), Indium-111 chloride (InCl
3), lithium perchlorate (LiClO
4) and various protonic acid such as trifluoromethanesulfonic acid, sal enixum (KHSO
4) etc.Reaction solvent is conventional organic solvent such as normal hexane, hexanaphthene, toluene, tetrahydrofuran (THF), methylene dichloride, dimethyl sulfoxide (DMSO), N, dinethylformamide, 1,4-dioxane, acetone, ether, acetonitrile etc.; Temperature of reaction is 0～70 ℃; Reaction times is 0.5～48 hour.
The present invention is a catalyzer with Lewis acid, and to 1, twice nucleophilic addition of 2-connection ketenes synthesizes Beta-methyl-β, beta-double indolene compound by indoles.Simple to operate, be a kind of method easily and effectively.Have following characteristics: (1) raw material conveniently is easy to get, and is simple to operate, convenient post-treatment.(2) reaction yield is higher.(3) conversion unit is simple, is easy to suitability for industrialized production.
Embodiment
Following examples help to understand the present invention, but are not limited to content of the present invention:
Embodiment 1
The preparation of the two indoles undecanes of (1) 2,2--4-ketone:
Operate as follows: (146mg, 1.25mmol) and 1, (83mg 0.5mmol) is dissolved in the Sc (OTf) that adds 5mol% in the acetonitrile of 2mL to 2-11 diene-4-ketone with indoles
3(12mg) stirring at room is 2 hours, and TLC follows the tracks of reaction to finishing, and is spin-dried for solvent, and directly (sherwood oil: ethyl acetate=5: 1) purifying obtains 119mg 2, the two indoles undecanes of 2--4-ketone, productive rate 60% to column chromatography.Liquid;
1HNMR (300MHz, CDCl
3): δ 8.09 (brs, 2H), 7.39 (d, J=8.4Hz, 2H), 7.31 (d, J=8.4Hz, 2H), 7.11 (t, J=7.8Hz, 2H), 7.00 (d, J=2.4Hz, 2H), 6.91 (t, J=7.8Hz, 2H), 3.52 (s, 2H), 2.04 (s, 3H), 1.82 (t, J=7.2Hz, 2H), 1.37-0.85 (m, 10H), 0.87 (t, J=6.6Hz, 3H);
13CNMR (75MHz, CDCl
3): δ 211.9,136.9, and 125.9,122.8,121.5,121.3,120.8,118.8,111.2,52.1,44.6,37.9,31.6,28.78,28.74,27.4,23.3,22.5,14.1; IR (neat) 3413,1697cm
-1MSm/z (%) 84 (100), 400 (M
+, 2.11); HRMSm/z (MALDI) calculated value, C
27H
32N
2ONa
+(M
++ Na) 423.2407. measured value: 423.2408.
Embodiment 2
The preparation of the two 5-methoxyl group indoles undecanes of (2) 2,2--4-ketone:
Operate as follows: (184mg, 1.25mmol) and 1, (83mg 0.5mmol) is dissolved in the Sc (OTf) that adds 5mol% in the methylene dichloride of 2mL to 2-11 diene-4-ketone with 5-methoxyl group indoles
3(12mg) stirring at room is 1.5 hours, and TLC follows the tracks of reaction to finishing, and is spin-dried for solvent, and directly (sherwood oil: ethyl acetate=5: 1) purifying obtains 122mg 2, the two 5-methoxyl group indoles undecanes of 2--4-ketone, productive rate 53% to column chromatography.Solid; Fusing point: 144-145 ℃ (ethyl acetate/hexane);
1HNMR (300MHz, CDCl
3): δ 7.95 (brs, 2H), 7.20 (d, J=9.9Hz, 2H), 7.07 (t, J=2.7Hz, 2H), 6.79-6.71 (m, 4H), 3.62 (s, 6H), 3.43 (s, 2H), 1.97 (s, 3H), 1.78 (t, J=7.2Hz, 2H), 1.27-0.83 (m, 10H), 0.83 (t, J=6.6Hz, 3H);
13CNMR (75MHz, CDCl
3): δ 211.6,153.1, and 132.2,126.4,122.5,121.9,111.6,111.2,103.4,55.7,51.7,44.6,37.7,31.6,28.85,28.79,27.0,23.3,22.6,14.1; IR (neat) 3406,1697cm
-1MSm/z (%) 319 (100), 460 (M
+, 8.80); Anal. calculated value C
29H
36N
2O
3: C, 75.62; H, 7.88; N, 6.08; Measured value C, 75.38; H, 7.89; N, 6.00.
Embodiment 3
The preparation of the two 5-bromo indole undecanes of (3) 2,2--4-ketone:
Operate as follows: (245mg, 1.25mmol) and 1, (83mg 0.5mmol) is dissolved in the In (OTf) that adds 5mol% in the acetonitrile of 2mL to 2-11 diene-4-ketone with the 5-bromo indole
3(12mg) stirring at room is 2 hours, and TLC follows the tracks of reaction to finishing, and is spin-dried for solvent, and directly (sherwood oil: ethyl acetate=5: 1) purifying obtains 155mg 2, the two 5-bromo indole undecanes of 2--4-ketone, productive rate 56% to column chromatography.Solid; Fusing point: 76-77 ℃ (ethylacetate/hexane);
1HNMR (300MHz, CDCl
3): δ 8.15 (brs, 2H), 7.37 (s, 2H), 7.21-6.99 (m, 6H), 3.40 (s, 2H), 1.96 (s, 3H), 1.84 (t, J=7.5Hz, 2H), 1.28-0.83 (m, 10H), 0.83 (t, J=6.9Hz, 3H);
13CNMR (75MHz, CDCl
3): δ 211.3,135.6, and 127.4,124.5,122.8,122.4,122.0,112.9,112.2,51.7,44.8,37.5,31.6,28.83,28.77,27.2,23.4,22.5,14.0; IR (neat) 3430,1701cm
-1MSm/z (%) 417 (100), 556 (M
+(2x
79Br), 3.34), 558 (M
+(
79Br/
81Br), 6.42), 560 (M
+(2
81XBr), 3.36); HRMSm/z (MALDI) calculated value C
27H
30N
2O
79Br
2Na
+(M
++ Na) 579.0617. measured value: 579.0619.
Embodiment 4
The preparation of the two 5-benzyloxy indole undecanes of (4) 2,2--4-ketone:
Operate as follows: (261mg, 1.25mmol) and 1, (83mg 0.5mmol) is dissolved in the Sc (OTf) that adds 5mol% in the acetonitrile of 2mL to 2-11 diene-4-ketone with the 5-benzyloxy indole
3(12mg) 50 ℃ were stirred 0.5 hour, and TLC follows the tracks of reaction to finishing, and is spin-dried for solvent, and directly (sherwood oil: ethyl acetate=5: 1) purifying obtains 157mg 2, the two 5-benzyloxy indole undecanes of 2--4-ketone, productive rate 51% to column chromatography.Solid; Fusing point: 51-52 ℃ (ethyl acetate/hexane);
1HNMR (300MHz, CDCl
3): δ 7.87 (brs, 2H), 7.39-7.19 (m, 10H), 7.18 (d, J=8.4Hz, 2H), 6.98 (d, J=2.4Hz, 2H), 6.83-6.78 (m, 4H), 4.84 (s, 4H), 3.31 (s, 2H), 1.90 (s, 3H), 1.69 (t, J=7.35Hz, 2H), and 1.23-1.03 (m, 6H), 1.02-0.89 (m, 2H), 0.89-0.77 (m, 2H), 0.81 (t, J=7.2Hz, 3H);
13CNMR (75MHz, CDCl
3): δ 211.8,152.0, and 137.5,132.3,128.3,127.59,127.52,126.2,122.1,122.0,112.1,111.7,104.9,70.8,51.6,44.5,37.6,31.5,28.78,28.71,27.0,23.2,22.5,14.0; IR (neat) 3415,3376,1697cm
-1MSm/z (%) 91 (100), 612 (M
+, 0.85); HRMSm/z (MALDI) calculated value C
41H
44N
2O
3Na
+(M
++ Na) 635.3244. measured value: 635.3244.
Embodiment 5
The preparation of the two 1-skatole undecanes of (5) 2,2--4-ketone:
Operate as follows: (164mg, 1.25mmol) and 1, (83mg 0.5mmol) is dissolved in the Cu (OTf) that adds 5mol% in the toluene of 2mL to 2-11 diene-4-ketone with the 1-skatole
3(12mg) stirring at room is 2 hours, and TLC follows the tracks of reaction to finishing, and is spin-dried for solvent, and directly (sherwood oil: ethyl acetate=5: 1) purifying obtains 130mg 2, the two 1-skatole undecanes of 2--4-ketone, productive rate 61% to column chromatography.Liquid;
1HNMR (300MHz, CDCl
3): δ 7.36 (d, J=8.1Hz, 2H), 7.24 (d, J=8.1Hz, 2H), 7.11 (t, J=8.1Hz, 2H), 6.91-6.82 (m, 4H), 3.71 (s, 6H), 3.44 (s, 2H), 1.98 (s, 3H), 1.71 (t, J=7.05Hz, 2H), 1.26-0.77 (m, 13H);
13CNMR (75MHz, CDCl
3): δ 211.5,137.6, and 126.4,126.1,121.4,121.1,118.3,109.2,52.3,44.5,38.0,32.7,31.6,28.8,28.7,27.7,23.2,22.5,14.1; IR (neat) 1703cm
-1MSm/z (%) 84 (100), 428 (M
+, 4.58); HRMSm/z (MALDI) calculated value, C
29H
36N
2ONa
+(M
++ Na) 451.2720. measured value: 451.2717.
Embodiment 6
The preparation of the two indoles decane of (6) 2,2--4-ketone:
Operate as follows: (146mg, 1.25mmol) and 1, (76mg 0.5mmol) is dissolved in the Sc (OTf) that adds 5mol% in the tetrahydrofuran (THF) of 2mL to 2-decadiene-4-ketone with indoles
3(12mg) stirring at room is 2 hours, and TLC follows the tracks of reaction to finishing, and is spin-dried for solvent, and directly (sherwood oil: ethyl acetate=5: 1) purifying obtains 122mg2, the two indoles decane of 2--4-ketone, productive rate 63% to column chromatography.Liquid;
1HNMR (300MHz, CDCl
3): δ 8.08 (brs, 2H), 7.38 (d, J=8.1Hz, 2H), 7.32 (d, J=8.1Hz, 2H), 7.10 (t, J=7.5Hz, 2H), 7.00 (d, J=2.7Hz, 2H), 6.90 (t, J=7.5Hz, 2H), 3.52 (s, 2H), 2.03 (s, 3H), 1.81 (t, J=7.5Hz, 2H), 1.29-0.78 (m, 11H);
13CNMR (75MHz, CDCl
3): δ 211.9,136.9, and 125.9,122.8,121.5,121.3,120.8,118.8,111.2,52.1,44.6,37.9,31.3,28.4,27.4,23.2,22.3,14.0; IR (neat) 3413,1697cm
-1MSm/z (%) 84 (100), 386 (M
+, 2.03); HRMSm/z (MALDI) calculated value, C
26H
30N
20Na
+(M
++ Na) 409.2250. measured value: 409.2254.
Embodiment 7
The preparation of the two indoles of (7) 4,4--1-phenyl pentane-2-ketone:
Operate as follows: with indoles (146mg, 1.25mmol) and 1,2-pentadiene-5-phenyl-4-ketone (79mg, 0.5mmol) being dissolved in HOTf (12mg) stirring at room 12 hours that adds 5mol% in the acetonitrile of 2mL, TLC follows the tracks of reaction to finishing, and is spin-dried for solvent, direct column chromatography (sherwood oil: ethyl acetate=5: 1) purifying, obtain 154mg 4, the two indoles of 4--1-phenyl pentane-2-ketone, productive rate 78%.Solid; Fusing point: 80-81 ℃ (ethylacetate/hexane);
1HNMR (300MHz, CDCl
3): δ 8.04 (brs, 2H), 7.36-7.3 1 (m, 4H), 7.20-7.06 (m, 7H), 6.88 (t, J=7.5Hz, 2H), 6.69-6.64 (m, 2H), 3.51 (s, 2H), 2.97 (s, 2H), 2.00 (s, 3H);
13CNMR (75MHz, CDCl
3): δ 209.0,136.9, and 133.9,129.4,128.27,128.23,126.6,125.8,122.39,122.36,121.5,121.4,120.8,118.9,111.4,51.5,51.2,38.1,27.4; IR (neat) 3414,1705cm
-1MSm/z (%) 259 (100), 392 (M
+, 11.27); HRMSm/z (MALDI) calculated value, C
27H
24N
2ONa
+(M
++ Na) 415.1781. measured value: 415.1786.
Embodiment 8
(8) preparation of 2-indoles-2-(1-skatole) undecane-4-ketone:
Operate as follows: (84.9mg, 0.3mmol), (59.0mg 0.45mmol) is dissolved in the KHSO that adds 5mol% in the acetonitrile of 2mL to the 1-skatole with (E)-2-indoles-2-hendecene-4-ketone
4(7.4mg) stirring at room is 3 hours, and TLC follows the tracks of reaction to finishing, and is spin-dried for solvent, and directly (sherwood oil: ethyl acetate=5: 1) purifying obtains 79.4mg 2-indoles-2-(1-skatole) undecane-4-ketone, productive rate 64% to column chromatography.Liquid;
1HNMR (300MHz, CDCl
3): δ 8.06 (brs, 1H), 7.43-7.22 (m, 4H), 7.17-7.05 (m, 2H), 7.02 (d, J=2.7Hz, 1H), 6.93-6.84 (m, 3H), 3.74 (s, 3H), 3.49 (s, 2H), 2.02 (s, 3H), 1.77 (t, J=7.35Hz, 2H), 1.26-O.80 (m, 13H);
13CNMR (75MHz, CDCl
3): δ 211.5,137.6, and 137.0 126.4,126.1,126.0,123.0,121.5,121.4,121.3,121.1,120.99,120.94,118.9,118.4,111.2,109.2,52.2,44.6,38.0,32.6,31.6,28.81,28.76,27.6,23.3,22.5,14.0; IR (neat) 3415,1703cm
-1MSm/z (%) 273 (100), 414 (M
+, 6.96); HRMSm/z (MALDI) calculated value, C
28H
34N
2ONa
+(M
++ Na) 437.2563. measured value: 437.2564.
Embodiment 9
(9) preparation of 2-indoles-2-(5-skatole) undecane-4-ketone:
Operate as follows: (84.9mg, 0.3mmol), (59.0mg 0.45mmol) is dissolved in the Sc (OTf) that adds 5mol% in the acetonitrile of 2mL to the 5-skatole with (E)-2-indoles-2-hendecene-4-ketone
3(7.4mg) stirring at room is 3 hours, and TLC follows the tracks of reaction to finishing, and is spin-dried for solvent, and directly (sherwood oil: ethyl acetate=5: 1) purifying obtains 96.9mg 2-indoles-2-(5-skatole) undecane-4-ketone, productive rate 78% to column chromatography.White solid; Fusing point: 59-60 ℃ (ethyl acetate/hexane);
1HNMR (300MHz, CDCl
3): δ 8.28 (brs, 1H), 8.16 (brs, 1H), 7.63 (dd, J
1=7.5Hz, J
2=21.3Hz, 1H), 7.55-7.38 (m, 3H), 7.33 (q, J=5.0Hz, 1H), 7.20-7.06 (m, 4H), 3.74 (t, J=5.0Hz, 2H), 2.54 (d, J=7.2Hz, 3H), 2.23 (s, 3H), 2.03 (t, J=7.35Hz, 2H), 1.53-1.02 (m, 13H); IR (neat) 3411,1696cm
-1MSm/z (%) 273 (100), 414 (M
+, 8.53); HRMSm/z (EI) calculated value, C
28H
34N
2O414.26711. measured value: 414.26380.
Claims (6)
1, a kind of β of following structural formula--methyl-β, beta-double indolene compound:
Or
2, a kind of β as claimed in claim 1--methyl-β, the synthetic method of beta-double indolene compound, it is characterized in that in organic solvent and 0～70 ℃ of condition under, with indoles or derivatives thereof, 1,2-connection ketenes and lewis acid catalyst reaction 0.5～48 hour, obtain β, beta-double indolene compound, wherein, indoles or derivatives thereof, 1, the mol ratio of 2-connection ketenes and lewis acid catalyst is 0.2～10: 1: 0.001～10.0.
3, β as claimed in claim 2--methyl-β, the synthetic method of beta-double indolene compound is characterized in that described catalyzer Lewis acid is trifluoromethanesulfonic acid scandium, copper trifluoromethanesulfcomposite, trifluoromethanesulfonic acid indium, trifluoromethanesulfonic acid zinc, Indium-111 chloride, lithium perchlorate or protonic acid.
4, β as claimed in claim 3--methyl-β, the synthetic method of beta-double indolene compound is characterized in that described protonic acid is trifluoromethanesulfonic acid or sal enixum.
5, β as claimed in claim 2--methyl-β, the synthetic method of beta-double indolene compound, it is characterized in that described organic solvent is normal hexane, hexanaphthene, toluene, tetrahydrofuran (THF), methylene dichloride, dimethyl sulfoxide (DMSO), N, dinethylformamide, 1,4-dioxane, acetone, ether or acetonitrile.
6, a kind of β as claimed in claim 1--methyl-β, the purposes of beta-double indolene compound is characterized in that being used for synthetic contain β, the bioactive compounds of beta-double indolene.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5428175A (en) * | 1993-02-22 | 1995-06-27 | Snow Brand Milk Products Co., Ltd. | Physiologically active compound |
| WO2000053313A2 (en) * | 1999-03-09 | 2000-09-14 | Arqule, Inc. | Lanthanide catalysts for synthesis of compounds and combinatorial libraries |
| US6841685B2 (en) * | 2000-06-07 | 2005-01-11 | State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Oregon State University | Methods for making bis-heterocyclic alkaloids |
-
2005
- 2005-01-27 CN CNB2005100236335A patent/CN1331854C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5428175A (en) * | 1993-02-22 | 1995-06-27 | Snow Brand Milk Products Co., Ltd. | Physiologically active compound |
| WO2000053313A2 (en) * | 1999-03-09 | 2000-09-14 | Arqule, Inc. | Lanthanide catalysts for synthesis of compounds and combinatorial libraries |
| US6841685B2 (en) * | 2000-06-07 | 2005-01-11 | State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Oregon State University | Methods for making bis-heterocyclic alkaloids |
Non-Patent Citations (1)
| Title |
|---|
| Novel indium-mediated ternaryreactions between indole-3-carboxaldehydes-allylbromide-enamines:facile synthesis of bisindolyl-and indolyl-heterocyclic alkanes Subodh Kumar,et al,Tetrahedron letters,Vol.44 2003 * |
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| Publication number | Publication date |
|---|---|
| CN1680319A (en) | 2005-10-12 |
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