CN104910090B - Dihydro-isoxazole class compound and its synthetic method - Google Patents
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- C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
- C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
- C07D261/04—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
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- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
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Abstract
The present invention relates to a kind of synthetic method of dihydro-isoxazole class compound, the structural formula of the compound is：R1=phenyl, aminomethyl phenyl, acetylphenyl, cyclohexyl, N (4 tosyl), indyl；R2=butyl ester base, amide groups, benzenesulfonyl；R2,
Description
Technical field
The present invention relates to a kind of dihydro-isoxazole class compound and its synthetic method.
Background technology
Dihydro-isoxazole class compound, because it has higher bioactivity and potential physiological and pharmacological activity, by people
Extensive concern.For example, the medicine containing dihydro-isoxazole skeleton is used as a kind of efficient treatment gram-positive bacteria institute
The antimicrobial of the infection caused（See reference document：Barbachyn, M. R. et al.J. Med. Chem.2003, 46,
284）.Dihydro-isoxazole class compound or a kind of effective antituberculotic（See reference document：Tangallapally, R.
P. et al.Bioorg. Med. Chem. Lett. 2007, 17, 6638）.In addition to the application in medicine, dihydro is different
Oxazole compounds are also the important herbicide of a class.（See reference document：S Ku Disi;E bar Aumanns;W Feng Deen etc.
2003,CN1402723）.In addition, dihydro-isoxazole class compound is also widely used in organic micromolecule ligand.For example,
Organic phenodiazine bidentate ligand with two dihydro-isoxazole class skeletons can be used in organic asymmetric syntheses, and in the reaction
Being proved to the chiral control to reaction has good effect.（See reference document：Arai, M. A. et al. J. Am. Chem. Soc.2001, 123, 2907）.
In addition, dihydro-isoxazole class compound or the highly useful organic synthesis building block of a class, available for building
Structure other organic compounds more complicated and changeable.For example, Curran utilizes Raney's nickel in NaAc_HAc buffer solution
The ring-opening reaction of dihydro-isoxazole ring is realized under help, beta-hydroxy ketone compounds are obtained（See reference document：Curran, D.
P. J .Am. Chem. Soc. 1983, 105, 5826）.
The method for the single cyano compound in synthesizing aryl pyrimidine ortho position reported in document mainly has following several：
（One）Sasaki et al. is sent out using ω-chloro isonitrosoacetophenone and acrylonitrile in triethylamine and ether solvent
Raw cycloaddition reaction, obtains 3- benzyl -5- cyano group dihydro-isoxazoles.But the Material synthesis of this method is complex（See reference
Document：Sasaki, T. etal. Bull. Chem. Soc. Jpn. , 1971, 44, 185-189）.
（Two）Kozikowski et al. with the help of isocyanates and triethylamine, completes intramolecular with nitro compound
Cyclization, synthesized dihydro-isoxazole class compound.But this method equally exists the shortcomings of Material synthesis is complicated（See ginseng
Examine document：Kozikowski, A. P.; Steint, P. D.J. Am. Chem. Soc.1982, 104, 4023）.
（Three）Itoh et al. then uses acetone or acetophenone as solvent and under the promotion of ammonium ceric nitrate, occurs three groups with alkene
Divide reaction, synthesize the dihydro-isoxazole class compound of class acetyl or benzoyl base substitution.But this method is to substrate
Scope has larger limitation, and causes to waste using excessive raw material（See reference document：Itoh, K. et al.
Tetrahedron Lett. 2002, 43, 7035）.
(4) Schmidt et al. is to replace second ketone compounds to be that raw material and phenylacetylene are synthesized by three steps, and one kettle way is obtained
To target product（See reference document：Schmidt, E. Y. etal.Org. Lett.2013, 15, 104）.
In summary, the synthetic method of dihydro-isoxazole class compound has the above several, but the substrate of these reactions is all
It is relatively complicated, often to be obtained by the reaction of several steps.Also, these reactions generally require to compare using strong acid or highly basic etc.
Exacting terms.
The content of the invention
An object of the present invention is to provide a kind of dihydro-isoxazole compound of 3- acyl groups substitution.
The second object of the present invention is the synthetic method for providing the compound.
To reach above-mentioned purpose, the reaction mechanism that the inventive method is used for：
。
According to above-mentioned reaction mechanism, present invention employs following technical scheme：
A kind of dihydro-isoxazole class compound, it is characterised in that the structural formula of the compound is：
R1=phenyl, aminomethyl phenyl ,-Ac-Ph, cyclopropyl ,-Ts-indolyl；
R2 = CO2Bu、CONH2、SO2Ph or；
R3 = 。
A kind of method for preparing above-mentioned dihydro-isoxazole class compound, it is characterised in that this method has following steps：
Under an inert atmosphere, alkynes, alkene, copper nitrate, alkyl nitrile compounds are pressed 1：（1.0~8.0）：（2.0~8.0）：（2.0
~10.0）Mol ratio be added in benzonitrile solvent, in 60oStirring reaction to reaction raw materials disappear under C；After reaction terminates,
Washed respectively with water and saturated aqueous common salt, product is extracted with ethyl acetate, organic phase obtains crude product after removing solvent；This is slightly produced
Thing obtains dihydro-isoxazole class compound through separating-purifying；The structural formula of described alkynes is：；Described alkene
Structural formula be：。
Above-mentioned alkyl nitrile compounds are C3~C6 direct-connected or side chain nitrile compounds.
The substituted dihydro-isoxazole class compound of the present invention is the important organic reaction intermediate of a class, passes through inhomogeneity
The organic chemical reactionses of type, such as ring-opening reaction, addition reaction, substitution reaction, can quickly and easily synthesize a series of virtue
Dihydro-isoxazole analog derivative, relevant reaction is exemplified below：Substitution product after the deprotection of such compound is that a class has
The medicine of antimuscarinic activity（See reference document：De Amici, M., Conti, P., Vistoli, G., Carrea,
G., Ottolina, G., De Micheli, C., Med. Chem. Res. 2001, 10, 615）；Boehringer
What is replaced after the deprotection that the GPR119 antagonists of Ingelheim companies exploitation also include such compound contains dihydro-isoxazole
[5,6] spirocyclic ring scaffold of ring（See reference document：Wellenzohn, B., Lessel, U., Beller, A.,
Isambert, T., Hoenke, C., Nosse, B., J. Med. Chem. 2012, 55, 11031）.
The inventive method raw material is simple and easy to get, and has best under the promotion of copper as nitrogen source and oxygen source using copper nitrate
Reactivity.Reaction has been used in the reaction dissolvent of routine, simple to operate, mild condition, reaction environmental protection, yield when excellent
Show, there is good development prospect in the industrial production.
Embodiment
Embodiment one：3- benzoyl -4,5- dihydro-isoxazole base -5- butyl carboxylates
3- benzoyl -4,5- dihydro-isoxazole base -5- butyl carboxylates use following step：1. in 1000 milliliters of reactors
15.3 grams of phenylacetylenes of middle addition, 28.9 grams of n-butyl acrylates, 72.5 grams of copper nitrates, 25.0 grams of propionitrile additives, 750 milliliters of benzene
Formonitrile HCN, is heated to 60 DEG C.Tracked and reacted with thin-layer chromatography method, disappeared to reaction raw materials；2. after reaction terminates, into system
Add water and reaction is quenched, product is extracted with ethyl acetate, organic phase is removed through saturated common salt water washing after drying with Rotary Evaporators
Solvent, obtains crude product；3. crude product column chromatography（Petroleum ether:Ethyl acetate=30: 1）Purifying, obtains 34.45 grams of 3- benzene
Formoxyl -4,5- dihydro-isoxazole base -5- butyl carboxylates, yield is 83%.
-11744, 1655, 1582, 1261, 1205, 704.
1H NMR (CDCl3, 500 MHz): δ 8.21 (d, J = 7.5 Hz, 2H), 7.61 (t, J = 7.5
Hz, 1H), 7.48 (t, J = 7.5 Hz, 2H),5.19 (dd, J = 11.5, 8.0 Hz, 1H),4.23 (t, J
= 6.5 Hz, 2H), 3.70-3.59 (m, 2H), 1.71-1.65 (m, 2H), 1.44-1.36 (m, 2H), 0.94
(t, J = 7.5 Hz, 3H).
13C NMR (CDCl3, 125 MHz): δ185.6, 169.3, 157.0, 135.6, 134.1, 130.5,
128.6, 79.2, 66.2, 8.6, 30.6, 19.1, 13.8.
LC-MS (MALDI/DHB) m/z: 298 [M+Na].
HRMS (MALDI/DHB) m/z:calcd for C15H17NO4Na [M+Na] 298.1050, found
298.1050.
Embodiment two： 3-（4- Methyl-benzoyls）- 4,5- dihydro-isoxazole base -5- butyl carboxylates
3-（4- Methyl-benzoyls）- 4,5- dihydro-isoxazole base -5- butyl carboxylates use following step：1. 1000
Milliliter reactor in add 17.4 grams of 4- methyl phenylacetylenes, 28.9 grams of n-butyl acrylates, 72.5 grams of copper nitrates, 25.0 grams just oneself
Nitrile additive, 500 milliliters of benzonitriles, is heated to 60 DEG C.Tracked and reacted with thin-layer chromatography method, disappeared to reaction raw materials；2. it is anti-
After should terminating, added water into system and reaction is quenched, product is extracted with ethyl acetate, organic phase is dried through saturated common salt water washing
Remove solvent with Rotary Evaporators afterwards, obtain crude product；3. crude product column chromatography（Petroleum ether:Ethyl acetate=30: 1）It is pure
Change, obtain 32.00 grams of 3-（4- Methyl-benzoyls）- 4,5- dihydro-isoxazole base -5- butyl carboxylates, yield is 74%.
-11744, 1651, 1604, 1261, 1202, 900, 740.
1H NMR (CDCl3, 500 MHz): δ 8.12 (d, J = 8.5 Hz, 2H), 7.26 (d, J = 8.5
Hz, 2H), 5.16 (dd, J = 11.5, 7.5 Hz, 1H), 4.21 (t, J = 6.7 Hz, 2H), 3.69-3.57
(m, 2H), 2.41 (s, 3H), 1.69-1.64 (m, 2H), 1.43-1.35 (m, 2H), 0.93 (t, J = 7.5
Hz, 3H).
13C NMR (CDCl3, 125 MHz): δ185.1, 169.4, 157.0, 145.1, 133.0, 130.6,
129.3, 79.0, 66.1, 38.8, 30.6, 21.9, 19.1, 13.8.
EI-MS m/z (%):289 (3) [M+], 119 (100), 91 (33), 57 (18).
HRMS (ESI) m/z:calcd for C16H20NO4 [M+H] 290.1387, found 290.1384.
Embodiment three： 3-（4- acetylbenzene formoxyls）- 4,5- dihydro-isoxazole base -5- butyl carboxylates
3-（4- acetylbenzene formoxyls）- 4,5- dihydro-isoxazole base -5- butyl carboxylates use following step：1. 1000
21.7 grams of 4- acetylenylbenzene ethyl ketones, 346.8 grams of n-butyl acrylates, 145.0 grams of copper nitrates, 25.0 grams are added in milliliter reactor
The own nitrile additives of 2-, 750 milliliters of benzonitriles are heated to 60 DEG C.Tracked and reacted with thin-layer chromatography method, disappeared to reaction raw materials；
2. reaction terminate after, added water into system and reaction be quenched, product is extracted with ethyl acetate, organic phase through saturated common salt water washing,
Remove solvent with Rotary Evaporators after drying, obtain crude product；3. crude product column chromatography（Petroleum ether:Ethyl acetate=5:
1）Purifying, obtains 33.65 grams of 3-（4- acetylbenzene formoxyls）- 4,5- dihydro-isoxazole base -5- butyl carboxylates, yield is 71%.
-11742, 1688, 1656, 1582, 1259, 1204, 904, 858.
1H NMR (CDCl3, 500 MHz): δ 8.28 (d, J = 8.5 Hz, 2H), 8.02 (d, J = 8.5
Hz, 2H), 5.21 (dd, J = 11.5, 8.5 Hz, 1H), 4.23 (t, J = 7.0 Hz, 2H), 3.69-3.59
(m, 2H), 2.65 (s, 3H), 1.70-1.65 (m, 2H), 1.44-1.36 (m, 2H), 0.94 (t, J = 7.0
Hz, 3H).
13C NMR (CDCl3, 125 MHz): δ 197.6, 185.0, 169.1, 157.0, 140.6, 138.7,
130.7, 128.3, 79.4, 62.3, 38.2, 30.6, 27.0, 19.1, 13.8.
EI-MS m/z (%): 317 (1) [M+], 147 (100)。
calcd for C17H20NO5 [M+H] 318.1336, found 318.1328.
Example IV：3- cyclopropyl acyl -4,5- dihydro-isoxazole base -5- butyl carboxylates
3- cyclopropyl acyl -4,5- dihydro-isoxazole base -5- butyl carboxylates use following step：1. in 1000 milliliters of reactions
9.9 grams of cyclopropyl acethlenes, 346.8 grams of n-butyl acrylates, 145.0 grams of copper nitrates, 125.0 grams of n-Butyronitrile additions are added in kettle
Thing, 600 milliliters of benzonitriles, is heated to 60 DEG C.Tracked and reacted with thin-layer chromatography method, disappeared to reaction raw materials；2. reaction terminates
Afterwards, added water into system and reaction is quenched, product is extracted with ethyl acetate, organic phase is through saturated common salt water washing, with rotation after drying
Turn evaporimeter and remove solvent, obtain crude product；3. crude product column chromatography（Petroleum ether:Ethyl acetate=30: 1）Purifying, is obtained
To 19.30 grams of 3- cyclopropyl acyl -4,5- dihydro-isoxazole base -5- butyl carboxylates, yield is 54%.
-11746, 1677, 1585, 1409, 1216, 989, 915.
1H NMR (CDCl3, 500 MHz): δ 5.17 (t, J = 10.0 Hz, 1H), 4.21 (t, J = 6.5
Hz, 2H), 3.41 (d, J = 8.5 Hz, 2H), 2.86-2.81 (m, 1H), 1.69-1.63 (m, 2H),
1.42-1.35 (m, 2H), 1.21-1.18 (m, 2H), 1.08-1.05 (m, 2H), 0.94 (t, J = 7.0 Hz,
3H).
13C NMR (CDCl3, 125 MHz): δ 194.6, 169.3, 157.6, 80.1, 66.2, 39.9,
30.6, 19.1, 18.4, 13.8, 12.7, 12.6.
LC-MS (ESI) m/z: 262 [M+Na].
HRMS (ESI) m/z:calcd for C12H17NNaO4 [M+Na] 262.1050, found 262.1050.
Embodiment five： 3-（1- (4- tosyls) -1H- indoles -3- acyl groups）- 4,5- dihydro-isoxazole base -5- carboxylic acids
Butyl ester
3-（1- (4- tosyls) -1H- indoles -3- acyl groups）Under -4,5- dihydro-isoxazole base -5- butyl carboxylates use
State step：1. 44.3 grams of 1- are added in 1000 milliliters of reactors（4- tosyls）3- acetenyls -1H- indoles, 28.9 grams
N-butyl acrylate, 290 grams of copper nitrates, 50.0 grams of isobutyronitrile additives, 500 milliliters of benzonitriles are heated to 60 DEG C.Use thin layer
Chromatography method tracking reaction, disappears to reaction raw materials；2. after reaction terminates, added water into system and reaction is quenched, use ethyl acetate
Product is extracted, organic phase removes solvent with Rotary Evaporators after drying, obtain crude product through saturated common salt water washing；3. crude product
Use column chromatography（Petroleum ether:Ethyl acetate=10: 1）Purifying, obtains 48.50 grams of 3-（1- (4- tosyls) -1H- Yin
Diindyl -3- acyl groups）- 4,5- dihydro-isoxazole base -5- butyl carboxylates, yield is 69%.
-13149, 1743, 1638, 1596, 1530, 1211, 1178, 972, 575.
1H NMR (CDCl3, 500 MHz): δ 8.90 (s, 1H), 8.35-8.33 (m, 1H), 7.98-7.96
(m, 1H), 7.86 (d, J = 8.5 Hz, 2H), 7.40-7.34 (m, 2H), 7.28 (d, J = 8.5 Hz,
2H), 5.21 (dd, J = 11.0, 8.5 Hz, 1H), 4.25 (t, J = 6.5 Hz, 2H), 3.69-3.59 (m,
2H), 2.36 (s, 3H), 1.72-1.67 (m, 2H), 1.45-1.38 (m, 2H), 0.96 (t, J = 7.5 Hz,
3H).
13C NMR (CDCl3, 125 MHz): δ 179.6, 169.4, 157.4, 146.1, 136.1, 134.7,
134.6, 130.4, 128.1, 127.5, 126.0, 125.2, 122.9, 118.3, 113.3, 79.1, 66.3,
38.1, 30.6, 21.8, 19.2, 13.8.
EI-MS m/z (%): 468 (19) [M+], 155 (36), 91 (50), 57 (100).
HRMS (ESI) m/z:calcd for C24H25N2O6S [M+H] 469.1428, found 469.1424.
Embodiment six：3- benzoyl -4,5- dihydro-isoxazole base -5- formamides
3- benzoyl -4,5- dihydro-isoxazole base -5- formamides use following step：1. in 1000 milliliters of reactors
Add 15.3 grams of phenylacetylenes, 85.3 grams of acrylamides, 72.5 grams of copper nitrates, 25.0 grams of positive valeronitrile additives, 500 milliliters of benzene first
Nitrile, is heated to 60 DEG C.Tracked and reacted with thin-layer chromatography method, disappeared to reaction raw materials；2. after reaction terminates, add into system
Water quenching is gone out reaction, and product is extracted with ethyl acetate, and organic phase removes molten after drying through saturated common salt water washing with Rotary Evaporators
Agent, obtains crude product；3. crude product column chromatography（Petroleum ether:Ethyl acetate=30: 1）Purifying, obtains 20.40 grams of 3- benzene first
Acyl group -4,5- dihydro-isoxazole base -5- formamides, yield is 62%.Fusing point：164-165oC。
-13393, 3144, 1698, 1654, 1572, 863.
1H NMR (d 6 -DMSO, 500 MHz): δ 8.05 (d, J = 7.0 Hz, 2H), 7.75 (s, 1H),
7.70 (t, J = 7.5 Hz, 1H), 7.56 (t, J = 7.5 Hz, 2H), 7.49 (s, 1H), 5.14 (dd, J
= 12.0, 7.0 Hz, 1H); 3.60 (dd, J = 17.5, 12.0 Hz, 1H), 3.43 (dd, J = 17.5,
7.0 Hz, 1H).
13C NMR (d 6 -DMSO, 125 MHz): δ 185.8, 170.8, 157.5, 135.6, 133.8,
129.9, 128.5, 80.2, 37.8.
LC-MS (MALDI/DHB) m/z: 241 [M+Na].
HRMS (MALDI/DHB) m/z:calcd for C11H10N2O3Na [M+Na] 241.0584, found
241.0584.
Embodiment seven：Phenyl-（5-（Benzenesulfonyl）- 4,5- dihydro-isoxazoles -3-）Ketone
Phenyl-（5-（Benzenesulfonyl）- 4,5- dihydro-isoxazoles -3-）Ketone uses following step：1. it is anti-at 1000 milliliters
Answer 15.3 grams of phenylacetylenes of addition, 25.3 grams of vinyl sulfuryl benzene, 72.5 grams of copper nitrates, 25.0 grams of 2- valeronitrile additives, 650 in kettle
Milliliter benzonitrile, is heated to 60 DEG C.Tracked and reacted with thin-layer chromatography method, disappeared to reaction raw materials；2. after reaction terminates, to
Added water in system and reaction is quenched, product is extracted with ethyl acetate, organic phase uses rotary evaporation through saturated common salt water washing after drying
Instrument removes solvent, obtains crude product；3. crude product column chromatography（Petroleum ether:Ethyl acetate=5: 1）Purifying, obtains 26.00
Gram phenyl-（5-（Benzenesulfonyl）- 4,5- dihydro-isoxazoles -3-）Ketone, yield is 55%.Fusing point：119-121oC。
-11654, 1590, 1316, 1277, 1153, 852, 680.
1H NMR (CDCl3, 500 MHz): δ 8.06-8.02 (m, 4H), 7.72 (t, J = 7.5 Hz,
1H), 7.61 (t, J = 7.5 Hz, 3H), 7.46 (t, J = 7.5 Hz, 2H), 5.57 (dd, J = 11.0,
4.5 Hz, 1H), 4.05 (dd, J = 19.5, 5.0 Hz, 1H), 3.84 (dd, J = 19.5, 115 Hz,
1H).
13C NMR (CDCl3, 125 MHz): δ 184.7, 157.4, 135.1, 135.0, 134.4, 130.5,
130.0, 129.6, 128.7, 93.5, 37.0.
LC-MS (ESI) m/z: 338 [M+Na].
HRMS (ESI) m/z:calcd for C16H13NNaO4S [M+Na] 338.0457, found 338.0449.
Embodiment eight：3- benzoyls -1- oxa- -2,8- diaza spiros [4.5] decyl- 2- alkene -8- carboxylic acid tert-butyl esters
3- benzoyls -1- oxa- -2,8- diaza spiros [4.5] decyl- 2- alkene -8- carboxylic acid tert-butyl esters use following step：
1. 15.3 grams of phenylacetylenes, 44.4 grams of n-butyl acrylates, 290.0 grams of copper nitrates, 25.0 grams are added in 1000 milliliters of reactors
The own nitrile additives of 3-, 500 milliliters of benzonitriles are heated to 60 DEG C.Tracked and reacted with thin-layer chromatography method, disappeared to reaction raw materials；
2. reaction terminate after, added water into system and reaction be quenched, product is extracted with ethyl acetate, organic phase through saturated common salt water washing,
Remove solvent with Rotary Evaporators after drying, obtain crude product；3. crude product column chromatography（Petroleum ether:Ethyl acetate=10:
1）Purifying, obtains 24.20 grams of 3- benzoyls -1- oxa-s -2,8- diaza spiro [4.5] decyl- 2- alkene -8- carboxylic acid tert-butyl esters, produces
Rate is 47%.Fusing point：131-132oC。
-11680, 1575, 1477, 1433, 1252, 1154, 1075, 937, 706.
1H NMR (CDCl3, 500 MHz): δ 8.20 (d, J = 7.0 Hz, 2H), 7.60 (t, J = 7.5
Hz, 1H), 7.47 (t, J = 8.0 Hz, 2H), 3.71-3.68 (m, 2H), 3.50-3.44 (m, 2H), 3.12
(s, 2H), 1.93-1.86 (m, 2H), 1.78-1.73 (m, 2H), 1.47 (s, 9H).
13C NMR (CDCl3, 125 MHz): δ 186.7, 157.8, 154.7, 135.8, 133.8, 130.4,
128.5, 87.3, 80.0, 44.2, 40.9, 35.9, 28.6.
LC-MS (ESI) m/z: 367 [M+Na].
Claims (1)
1. a kind of preparation method of dihydro-isoxazole class compound, the structural formula of the compound is：
R1=phenyl, aminomethyl phenyl or-Ac-Ph；
R2=CO2Bu、CONH2、SO2Ph or
It is characterized in that this method has following steps：Under an inert atmosphere, by alkynes, alkene, copper nitrate, alkyl nitrile chemical combination
Thing presses 1：(1.0~8.0)：(2.0~8.0)：The mol ratio of (2.0~10.0) is added in benzonitrile solvent, is stirred at 60 DEG C
Reaction to reaction raw materials are mixed to disappear；After reaction terminates, washed respectively with water and saturated aqueous common salt, product be extracted with ethyl acetate,
Organic phase obtains crude product after removing solvent；The crude product obtains dihydro-isoxazole class compound through separating-purifying；Described alkynes
The structural formula of hydrocarbon is：The structural formula of described alkene is：Described alkyl nitrile compounds be C3~
C6 direct-connected or side chain nitrile compounds.
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| Copper Nitrate Mediated Regioselective [2+2+1] Cyclization of Alkynes with Alkenes: A Cascade Approach to △2-Isoxazolines;Mingchun Gao et al.;《Angewandte Chemie, International Edition》;20150618;第54卷(第30期);8795-8799 * |
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| Ken-ichi Itoh et al..Application of silica gel-supported polyphosphoric acid (PPA/SiO2) as a reusable solid acid catalyst to the synthesis of 3-benzoylisoxazoles and isoxazolines.《Tetrahedron Letters》.2011,第52卷6892-6895. * |
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