CN1229367C - Furan 4alpha-methylol polyhydro naphthalene compound and its synthesis and use - Google Patents

Furan 4alpha-methylol polyhydro naphthalene compound and its synthesis and use Download PDF

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CN1229367C
CN1229367C CN 02151114 CN02151114A CN1229367C CN 1229367 C CN1229367 C CN 1229367C CN 02151114 CN02151114 CN 02151114 CN 02151114 A CN02151114 A CN 02151114A CN 1229367 C CN1229367 C CN 1229367C
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acid
furan
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methylol
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田伟生
丁凯
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

The present invention relates to a furan 4 alpha-methylol polyhydro naphthalene compound, a synthetic method and a use. The compound has the following structural formula, wherein R<1>, or R<2> or R<3> is equal to H or C1 to C3; R<2> and R<3> are equal to steroid; = represents a single bond or double bonds; the steroid is R<4> equal to H, or C1 to C4 or methoxymethyl. The present invention has the advantage of simple and convenient synthetic method, is suitable for industrial production and is capable of synthesizing marine natural products (+/-)spiniferin-1 with a structural formula and an analog thereof.

Description

Furan 4alpha-methylol polyhydro naphthalene compound, preparation method and use
Technical field
The present invention relates to multiple Furan 4alpha-methylol polyhydro naphthalene compound, preparation method and use.Can synthesize this compounds under the acid catalysis condition and with the carbonium ion rearrangement reaction method (referring to CN 97106576.4) that the fluoro sulfonic acid fluoride brings out, above-claimed cpd can synthesize marine natural product spiniferin-1 and analogue thereof efficiently.
Background technology
Natural spiniferin-1 is that Italian professor G.Cimino separates a kind of furans sesquiterpene (Tetra.Lett.1975 (45), 3727) that obtains from a kind of spongy biological pleraplysilla in gulf, Naples.1980, J.A.Marshall group determined its structure following (referring to J.Amer.Chem.Soc.1980 (102), 4274) by dihydro derivative (±) dihydrospiniferin-1 of synthetic spiniferin-1:
Figure C0215111400041
Figure C0215111400042
(±)spiniferin-1 (±)dihydrospiniferin-1
As everyone knows, there is the natural product that contains the cumarone structure in a large number in occurring in nature, and these natural products have physiologically active (Comprehensive Hetercycles Chemistry II) widely.Cycloheptatriene is the high-carbon homologue of benzene, and the spiniferin-1 with cyclohepta furan structure may have the physiological action similar to benzofuran compounds.
Figure C0215111400043
benzofuran?analog
Although the compound of this constructional feature only has spiniferin-1, it has represented the organic molecule of a class novel texture.Its structural instability is decomposed easily, and comparatively speaking, its pair hydroperoxide derivative dihydrospiniferin-1 is comparatively stable.Though the definite physiologically active of spiniferin-1 also fails to be studied, some organic molecules that contain the cumarone structural unit have been used as the fact of medicine, are enough to make us to pay close attention to the potential use of spiniferin-1.
Spiniferin-1 progress reason slowly is to obtain the sample difficulty.Nineteen eighty-three, U.S. professor J.A.Marshall has studied the synthetic of spiniferin-1 and two hydroperoxide derivatives thereof.But synthetic route is tediously long, and productive rate is very low, fails to solve for further studying the problem that enough samples are provided.
In research fluoro sulfonic acid fluoride reagent and the reaction of 19-hydroxy steroid, people such as Tian Weisheng have had been found that the tandem rearrangement reaction (CN 97106576.4) that an interesting carbonium ion causes
Figure C0215111400051
People such as Tian Weisheng also use this tandem rearrangement that has been found that reaction, have synthesized (±) dihydrospiniferin-1 (CN 02145067.6).
(±)dihydrospiniferin-1
But in the process of synthetic (±) spiniferin-1 and analogue thereof, use equally when tactful, fail to obtain target product, main problem is that the ozonization condition is too violent, and is influential to the functional group at other position of molecule.Therefore, still constantly explore new (±) spiniferin-1 and analogue thereof and can condition in gentleness under, efficient, the method for synthetic quickly and easily (±) spiniferin-1 and analogue thereof.
Summary of the invention
The object of the invention provides a series of Furan 4alpha-methylol polyhydro naphthalene compounds;
Another object of the present invention provides a kind of synthetic method of above-mentioned Furan 4alpha-methylol polyhydro naphthalene compound.Promptly use acid catalyzed cyclization to synthesize the Furan 4alpha-methylol polyhydro naphthalene compound;
The present invention also provides a kind of purposes of above-mentioned Furan 4alpha-methylol polyhydro naphthalene compound, can use synthetic marine natural product spiniferin-1 of this compound and multiple analogue thereof.
Furan 4alpha-methylol polyhydro naphthalene compound of the present invention has following structural formula:
Figure C0215111400061
Wherein, R=OH, OTHP or COOR 6, Be expressed as singly-bound or two key, R 1, R 2Or R 3=H or C1-C3, or R 2+ R 3=steroidal is as R 1=R 2=R 3=H; R 1=R 2=C1-C3, R 3=H; Or R 1=H or C1-C3, R 2+ R 3=steroidal.Described steroidal is
Figure C0215111400063
, R wherein 4=H, C1-C4 or methoxyl methyl, , n=0-2, R 6=H, C1-C4, THP are tetrahydropyrans.
Compound of the present invention can be example with the compound of following structural formula:
Figure C0215111400065
Figure C0215111400066
Or Deng,
R wherein 4=H, C1-C4 or methoxyl methyl, Or N=0-2.
The synthetic method of Furan 4alpha-methylol polyhydro naphthalene compound 4 of the present invention is used α, and beta unsaturated ketone is a raw material, THPOCH 2CHO is the addition segment, and two-step reaction has synthesized the Furan 4alpha-methylol polyhydro naphthalene compound.Reaction formula is as follows:
1 2
3 4，
Wherein-OPG is the potential functional group of hydroxyl, can be the hydroxyl of ester group or tetrahydropyrans protection.
Compound 3 de-protected methods are respectively reduction or acid hydrolysis becomes hydroxyl.
Described compound 1,2 and 3 structural formula are as follows:
Figure C0215111400071
Figure C0215111400073
Compound 1, compound 2, compound 3,
Wherein
Figure C0215111400074
For-COOMe ,-COOEt, CH 2OTHP, THP are the tetrahydropyrans protecting group, and above-claimed cpd also can further be described as respectively:
Compound 1:
Figure C0215111400075
Figure C0215111400076
Or
Figure C0215111400077
Compound 2:
Figure C0215111400078
Compound 3
Figure C02151114000710
Or
Figure C02151114000712
Above-claimed cpd, in 2,3, R 4=H, C1-C4 or methoxyl methyl,
Or
In the method for the present invention, addition segment THPOCH 2CHO can prepare (J.Amer.Chem.Soc.1995 (117), 634) by literature method.
Method of the present invention is with following 1) and 2); 1), 2) and 3) or 1), 2) and 4) three kinds of methods are synthetic, specific as follows:
1) under aprotic polar solvent neutralization-40-78 ℃ temperature, compound 1 and highly basic reaction 0.5-3 hour, the intermediate that obtains continues and ZnCl 2Reaction adds THPOCH 2CHO obtains compound 2, productive rate 90-100%; Wherein, described highly basic is N-Lithiodiisopropylamide or MN (SiMe 3) 2Deng, M=Li, Na, K, compound, highly basic, ZnCl 2And THPOCH 2The mol ratio of CHO is 1: 1-10: 1-4: 1-4;
2) in inert solvent, compound 2 reacted 0.5-10 hour under reflux temperature at 0 ℃ with acid, obtained compound 3, productive rate 70-90%, and described compound 2 is 1 with the mol ratio of acid: 0.1-0.5, described acid can be mineral acid or organic acid; Described mineral acid can be a haloid acid, sulfuric acid, and phosphoric acid etc., described organic acid can be formic acid, acetate, tosic acid, camphorsulfonic acid or tosic acid pyridinium salt etc.
3) in inert solvent, compound 3 and LiALH 4Reacted 0.5-2 hour under reflux temperature at 0 ℃, obtain compound 4, productive rate 70-90%, described compound 3 and LiALH 4Mol ratio be 1: 1-5.
4) in inert solvent, compound 3 reacted 0.5-5 hour under reflux temperature at 0 ℃ with acid, obtained compound 4, productive rate 70-90%, and described compound 3 is 1 with the mol ratio of acid: the described acid of 0.1-0.5 can be mineral acid or organic acid; Described mineral acid can be a haloid acid, sulfuric acid, and phosphoric acid etc., described organic acid can be formic acid, acetate, tosic acid, camphorsulfonic acid or tosic acid pyridinium salt etc.
Above-mentioned inert solvent can be ether, tetrahydrofuran (THF), sherwood oil, normal hexane, benzene, toluene, alcohol or halohydrocarbon etc.
Described aprotic polar solvent can be ether, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO) or dimethyl formamide etc.
Method provided by the invention has been synthesized a series of Furan 4alpha-methylol polyhydro naphthalene compounds, and structure is:
R wherein 1, R 2Or R 3=H or C1-C3, or R 2+ R 3=steroidal, Be expressed as singly-bound or two key, described steroidal is
Figure C0215111400091
R1=H wherein, C1-C4 or methoxyl methyl,
Figure C0215111400092
Or
Figure C0215111400093
Use patented method (CN 02145067.6), rearrangement reaction take place under the inducing of fluoro sulfonic acid fluoride reagent,
Can be converted into structural formula efficiently is Marine natural product spiniferin-1 and the analogue thereof of (±) spiniferin-1.The structure of this marine natural product (±) spiniferin-1 and analogue thereof is as follows:
Figure C0215111400096
R wherein 1, R 2Or R 3=H or C1-C3, or R 2+ R 3=steroidal, Be expressed as singly-bound or two key, wherein steroidal is
Figure C0215111400098
, R4=H wherein, C1-C4 or methoxyl methyl, Or
Invention major advantage of the present invention has:
1, use the easily α of preparation, beta unsaturated ketone is a raw material, uses ZnCl 2Catalytic aldol reaction obtains adduct, has made up furan nucleus under acid catalysis efficiently.The control reaction conditions can obtain the Furan 4alpha-methylol polyhydro naphthalene compound by very high productive rate.
2, furan nucleus is synthetic, has strengthened the electron density of 2 ethylene linkages, and the inducing that makes fluoro sulfonic acid fluoride reagent generation rearrangement reaction speed down accelerated greatly, need not to use instead under the stronger alkali room temperature and can react.Simplified test operation.
3, furan nucleus synthetic is equivalent to protect α, the carbonyl of beta unsaturated ketone.Simplified the synthetic of spiniferin-1 analogue.With the example that synthesizes of (±) dihydrospiniferin-1, further be reduced to for 4 steps (document was 13 steps, and patent (CN 02145067.6) was 6 steps), each goes on foot in the reaction yield good by the time.Do not use expensive reagent, all can buy in market.It is a synthetic route with industrial value.
Embodiment
To help to understand the present invention by following embodiment, but not limit content of the present invention.
Embodiment 1 compound 2a's is synthetic
Figure C0215111400101
0.26ml (2mmol) Diisopropylamine is dissolved in the 1ml tetrahydrofuran (THF), is cooled to-78 ℃, drips the n-BuLi of 1.0ml 2M (2mmol).Finish and stirred 15 minutes.
Under-78 ℃ slowly to the 2ml tetrahydrofuran solution that wherein drips 220mg (1mmol) compound 1a.-78 ℃ of following stirring reactions added 2mmol (2eq) ZnCl after 2 hours 2, stir 5min, add 2mmol (2eq) THPOCH 2CHO finishes, and reacts 1 hour.Saturated NH 4Cl solution cancellation reaction.Dichloromethane extraction.Merge organic phase, washing, saturated NaCl solution is washed Na 2SO 4Dry.Take out and desolvate, cross post and get 320mg compound 2a (productive rate 90%).
Compound 2a:C20H30O6 (366.45)
1H-NMR(CDCl 3，300MHz)：δ5.94(m，1H)，4.61(m，1H)，3.5-4.3(m，8H)，1.3-1.8(m，17H)1.28(m，3H)。
Embodiment 2 compound 3a's is synthetic
Figure C0215111400111
200mg (0.8mmol) compound 2a is dissolved in 4ml THF, adds the 20mg tosic acid, and 60 ℃ are stirred 3hr down.Take out and desolvate, residue is crossed post and is got 130mg (77%) colorless oil 3a.
Compound 3a:C15H18O3 (246.30)
1H-NMR(CDCl 3?300MHz)：δ7.17(d，1H，J＝1.8Hz)，6.24(s，1H)，6.19(d，1H，J＝1.8Hz)，4.0-4.2(m，2H)，3.20(d，1H，J＝16.5Hz)，2.59(d，1H，J＝16.2Hz)，)，1.3-2.5(m，8H)，1.19(t，3H，J＝7.2Hz)。
Embodiment 3 compound 4a's is synthetic
3a is dissolved in 2mlTHF with 100mg (0.4mmol) compound.Room temperature splashes into 40mg (2.5eq) LiAlH 45mlTHF suspension in, the reaction 0.5hr.Less water cancellation reaction is filtered, and boils off solvent, and residue gets 88mg compound 4a (100%) through column chromatography for separation.
Compound 4a:C13H16O2 (204.26)
m.p.92-93℃
1H-NMR(CDCl 3?300MHz)δ7.17(d，1H，J＝1.8Hz)，6.19(d，1H，J＝1.8Hz)，6.15(d，1H，J＝0.9Hz)，3.46(m，2H)，2.89(d，1H，J＝16.8Hz)，2.36(d，1H，J＝16.5Hz)，)，1.2-2.3(m，8H)。
Embodiment 4 compound 5a's is synthetic
Figure C0215111400113
90mg4a (0.44mmol) is dissolved in 3mlTHF, and 0 ℃ adds 150mg (2eq) DBU and 300mg (2eq) RfSO 2F stirs 0.5hr, walks board raw material and transforms fully.Reaction solution is drained, and crosses post, gets the colourless mucus 5a of 65mg (80%).
Compound 5a:C25H38O4 (402.57)
1H-NMR(CDCl 3?300MHz)δ7.34(d，1H，J＝1.8Hz)，6.57(d，1H，J＝2.1Hz)，3.09(d，1H，J＝10.8Hz)，2.55(m，2H)，2.35(m，2H)，1.86(m，2H)，1.24(d，1H，J＝11.2Hz)，1.18(m，2H)。
Embodiment 5 compound 2b's is synthetic
Under-78 ℃ slowly to 1.2eq (1.2mmol) LiN (SiMe 3) 22mlTHF solution in drip the 2ml tetrahydrofuran solution of 400mg (1mmol) compound 1b.-78 ℃ of following stirring reactions added 1mmol (leq) ZnCl after 2 hours 2, stir 5min, add 1mmol (leq) THPOCH 2CHO finishes, and reacts 1 hour.Saturated NH 4Cl solution cancellation reaction.Dichloromethane extraction.Merge organic phase, washing, saturated NaCl solution is washed Na 2SO 4Dry.Take out and desolvate, cross post and get 540mg compound 2b (productive rate 100%).
Compound 2b:C30H50O7 (546.74)
1H-NMR(CDCl 3，300MHz)：δ5.90(d，1H)，4.61(m，1H)，3.34(s，3H)，3.22(t，2H，J＝8.1Hz)0.79(s，3H)。
Embodiment 6 compound 4b's is synthetic
Figure C0215111400122
270mg (0.5mmol) compound 2b is dissolved in 2ml THF, adds 0.1ml 1N HCl, stirs 1hr under the room temperature.Take out and desolvate, residue is crossed post and is got 150mg (88%) colorless oil 4b.
Compound 4b:C22H30O3 (342.47)
1H-NMR(CDCl 3?300MHz)：δ7.16(d，1H，J＝2.1Hz)，6.25(d，1H，J＝1.5Hz)，6.18(s，1H)，3.87，(m，1H，3.66，(m，1H)，3.34(s，3H)，3.23(t，1H，J＝8.1Hz)，3.01(d，1H，J＝16.8Hz)，2.71(d，1H，J＝16.8Hz)，0.80(s，3H)。
Embodiment 7 compound 5b's is synthetic
70mg4b (0.2mmol) is dissolved in 2mlTHF, and 0 ℃ adds 30mg (leq) DBU and 60mg (leq) RfSO 2F stirs 0.5hr, walks board raw material and transforms fully.Reaction solution is drained, and crosses post, gets the colourless mucus 5b of 60mg (92%).
Compound 5b:C22H28O2 (324.46)
1H-NMR(CDCl 3?300MHz)δ7.32(d，1H，J＝2.1Hz)，6.55(d，1H，J＝2.1Hz)，6.27(s，1H)，6.27(s，1H)，6.22(s，3H)，3.29(d，1H，J＝10.2Hz)，3.27(t，1H，J＝8.1Hz)，1.14(d，1H，J＝10.5Hz)，0.92(s，1H)。
Embodiment 8 compound 2c's is synthetic
Figure C0215111400132
0.26ml (2mmol) Diisopropylamine is dissolved in the 1ml tetrahydrofuran (THF), is cooled to-78 ℃, drips the n-BuLi of 1.0ml 2M (2mmol).Finish and stirred 15 minutes.
Under-78 ℃ slowly to the 2ml tetrahydrofuran solution that wherein drips 220mg (1mmol) compound 1c.-40 ℃ of following stirring reactions added 1mmol (leq) ZnCl after 2 hours 2, stir 5min, add 1mmol (leq) THPOCH 2CHO finishes, and reacts 1 hour.Saturated NH 4Cl solution cancellation reaction.Dichloromethane extraction.Merge organic phase, washing, saturated NaCl solution is washed Na 2SO 4Dry.Take out and desolvate, cross post and get 310mg compound 2c (productive rate 85%).
Compound 2a:C20H28O6 (364.43)
1H-NMR(CDCl 3，300MHz)：δ6.29(s，2H)，5.88(d，1H，J＝1.8Hz)，4.63(m，1H)，4.19(m，2H)，1.24(m，3H)
Embodiment 9 compound 5c's is synthetic
200mg (0.55mmol) compound 2c is dissolved in 4ml THF, adds the 20mg tosic acid, and 60 ℃ are stirred 3hr down.Take out and desolvate, residue 230mg3c is directly used in the next step.
The 230mg crude product is dissolved in 10mlTHF.Room temperature splashes into 100mg (2.5eq) LiAlH 45mlTHF suspension in, the reaction 0.5hr.Less water cancellation reaction is filtered, and boils off solvent, and residue 200mg 4c is directly used in the next step.
The 200mg crude product is dissolved in 5mlTHF, and 0 ℃ adds 300mg (2eq) DBU and 600mg (2eq) RfSO 2F stirs 0.5hr, walks board raw material and transforms fully.Reaction solution is drained, and crosses post, gets the colourless mucus 5a of 80mg (three steps 79%).
Compound 5c:C13H12O (184.23)
1H-NMR(CDCl 3?300MHz)δ7.39(d，1H，J＝2.1Hz)，6.61(d，1H，J＝1.8Hz)，6.3-6.4(d，4H)，3.61(d，1H，J＝13.5Hz)，1.03(d，1H，J＝9.9Hz)

Claims (7)

1, a kind of Furan 4alpha-methylol polyhydro naphthalene compound has following structural formula:
R wherein 1, R 2Or R 3=H or C1-C3, or R 2+ R 3=steroidal,
Figure C021511140002C2
Be expressed as singly-bound or two key, steroidal is
Figure C021511140002C3
Or R 4=H, C1-C4 or methoxyl methyl, Or N=0-2.
2, Furan 4alpha-methylol polyhydro naphthalene compound as claimed in claim 1 is characterized in that having following structural formula:
Figure C021511140002C7
Or
R wherein 4=H, C1-C4 or methoxyl methyl,
Figure C021511140002C10
Or
Figure C021511140002C11
, n=0-2.
3, a kind of synthetic method of Furan 4alpha-methylol polyhydro naphthalene compound as claimed in claim 1 is characterized in that with following 1) and 2); 1), 2) and 3) or 1), 2) and 4) three kinds of methods are synthetic:
1) under aprotic polar solvent neutralization-40-78 ℃ temperature, compound 1 and highly basic reaction 0.5-3 hour, the intermediate that obtains continues and ZnCl 2Reaction adds THPOCH 2CHO, THP are the tetrahydropyrans protecting group, obtain compound 2; Wherein, described highly basic is N-Lithiodiisopropylamide or MN (SiMe 3) 2, M=Li, Na, K, compound, highly basic, ZnCl 2And THPOCH 2The mol ratio of CHO is l: l-10: 1-4: 1-4;
2) in inert solvent, compound 2 reacted 0.5-10 hour under reflux temperature at 0 ℃ with acid, obtained compound 3, and described compound 2 is 1 with the mol ratio of acid: 0.1-0.5;
3) in inert solvent, compound 3 and LiALH 4Reacted 0.5-2 hour under reflux temperature at 0 ℃, obtain compound 4, described compound 3 and LiALH 4Mol ratio be 1: 1-5;
4) in inert solvent, compound 3 reacted 0.5-5 hour under reflux temperature at 0 ℃ with organic or inorganic acid, obtained compound 4, and described compound 3 is 1 with the mol ratio of organic or inorganic acid: 0.1-0.5;
Wherein, compound 1,2,3 and 4 structural formula is as follows:
Figure C021511140003C1
Figure C021511140003C4
Compound 1, compound 2, compound 3, compound 4,
R in the above-claimed cpd 1R 2And R 3According to claim 1, wherein
Figure C021511140003C5
For-COOMe ,-COOEt ,-CH 2OTHP, THP are THP trtrahydropyranyl.
4, a kind of synthetic method of Furan 4alpha-methylol polyhydro naphthalene compound as claimed in claim 3 is characterized in that described aprotic polar solvent is ether, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO) or dimethyl formamide.
5, a kind of synthetic method of Furan 4alpha-methylol polyhydro naphthalene compound as claimed in claim 3 is characterized in that described inert solvent is ether, tetrahydrofuran (THF), sherwood oil, normal hexane, benzene, toluene, alcohol or halohydrocarbon.
6, a kind of synthetic method of Furan 4alpha-methylol polyhydro naphthalene compound as claimed in claim 3 is characterized in that described mineral acid can be a haloid acid, sulfuric acid, phosphoric acid, described organic acid can be formic acid, acetate, tosic acid, camphorsulfonic acid or tosic acid pyridinium salt.
7, a kind of purposes of Furan 4alpha-methylol polyhydro naphthalene compound as claimed in claim 1 is characterized in that being used for the following marine natural product of composite structure general formula:
Figure C021511140003C6
R wherein 1, R 2, R 3With
Figure C021511140003C7
According to claim 1.
CN 02151114 2002-12-06 2002-12-06 Furan 4alpha-methylol polyhydro naphthalene compound and its synthesis and use Expired - Fee Related CN1229367C (en)

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