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2016 Volume 36 Issue 8
2016, 36(8): 1715-1740
doi: 10.6023/cjoc201601009
Abstract:
Fluorine-containing groups have strong electron-withdrawing effect and high lipophilicity, organic molecules incorporated fluorine-containing groups can improve its function. Therefore, the incorporation of fluorine-containing groups into molecules has become the current research hotspot. The method for incorporation of CF3S group becomes one of the hot research field due to its excellent nature. The strategy for incorporation of CF3Se, CF3O and CF3CH2O groups has also been the attention of researchers. 18F has nearly ideal nuclear properties and is the most widely used positron emission tomography (PET) radioisotope for clinical imaging. Therefore, the development of new [18F]radiotracers becomes the research focus of many researchers. The method for 18F-labeling of biomolecules is the key to the development of new [18F]radiotracers. This paper mainly introduce the recently reported methodology of direct incorporating CF3X (X＝S, Se, O, CH2O) groups into molecules and some research results of 18F-labeling methods. Furthermore, some noteworthy research directions in this field are summarized.
Fluorine-containing groups have strong electron-withdrawing effect and high lipophilicity, organic molecules incorporated fluorine-containing groups can improve its function. Therefore, the incorporation of fluorine-containing groups into molecules has become the current research hotspot. The method for incorporation of CF3S group becomes one of the hot research field due to its excellent nature. The strategy for incorporation of CF3Se, CF3O and CF3CH2O groups has also been the attention of researchers. 18F has nearly ideal nuclear properties and is the most widely used positron emission tomography (PET) radioisotope for clinical imaging. Therefore, the development of new [18F]radiotracers becomes the research focus of many researchers. The method for 18F-labeling of biomolecules is the key to the development of new [18F]radiotracers. This paper mainly introduce the recently reported methodology of direct incorporating CF3X (X＝S, Se, O, CH2O) groups into molecules and some research results of 18F-labeling methods. Furthermore, some noteworthy research directions in this field are summarized.
2016, 36(8): 1741-1764
doi: 10.6023/cjoc201604009
Abstract:
The development of C—H bond activiation and the typical reaction mechanism is introduced in the first part. The progress of organic small molecule and polymer semiconductors prepared by C—H activation is reviewed. The applicability of C—H activation and the performance of organic semiconductors achieved by C—H activation are discussed in detail.
The development of C—H bond activiation and the typical reaction mechanism is introduced in the first part. The progress of organic small molecule and polymer semiconductors prepared by C—H activation is reviewed. The applicability of C—H activation and the performance of organic semiconductors achieved by C—H activation are discussed in detail.
2016, 36(8): 1765-1778
doi: 10.6023/cjoc201604010
Abstract:
The epoxidation catalyzed by transition metals (Cr, Ni, Co, Ru, Mn) has been received widespread attention over the past decades, and the corresponding epoxides are widely used in the synthesis of pharmaceuticals, fine chemicals and pesticides. Compared to other transition metals, metal Mn catalyst has been widely used in organic synthesis due to its inexpensive, environment-friendly, chemical stability and high catalytic activity. This paper reviews the recent progress on epoxidation of olefins catalyzed by the catalysts which were formed by the reaction of different valence metal Mn(II, III, and V) and different NXOY ligands in different oxidants/co-catalyst systems. At the same time, the Mn catalysts with different valence states are involved in the process of the epoxidation of olefins and the mechanism of how to transfer the oxygen of reactive intermediates to the olefins was discussed.
The epoxidation catalyzed by transition metals (Cr, Ni, Co, Ru, Mn) has been received widespread attention over the past decades, and the corresponding epoxides are widely used in the synthesis of pharmaceuticals, fine chemicals and pesticides. Compared to other transition metals, metal Mn catalyst has been widely used in organic synthesis due to its inexpensive, environment-friendly, chemical stability and high catalytic activity. This paper reviews the recent progress on epoxidation of olefins catalyzed by the catalysts which were formed by the reaction of different valence metal Mn(II, III, and V) and different NXOY ligands in different oxidants/co-catalyst systems. At the same time, the Mn catalysts with different valence states are involved in the process of the epoxidation of olefins and the mechanism of how to transfer the oxygen of reactive intermediates to the olefins was discussed.
2016, 36(8): 1779-1789
doi: 10.6023/cjoc201601020
Abstract:
Because of its unique structure and chemical characteristics, 1,2,3-triazole was increasingly considered as an important structural motif in pharmaceuticals, agrochemicals, dyes and materials. Recently, main progress has been achieved under transition metal-catalysis. Considering the toxicity and potentially environmental pollution of transition metals, the novel, efficient and convenient synthetic methodologies of 1,2,3-triazole under transition metal-free conditions have been received widely attention. Based on our work and research interesting, the aim of this review is to give an overview of the progress on the diverse synthetic methodologies of 1,2,3-triazole with transition metal-free since 2010.
Because of its unique structure and chemical characteristics, 1,2,3-triazole was increasingly considered as an important structural motif in pharmaceuticals, agrochemicals, dyes and materials. Recently, main progress has been achieved under transition metal-catalysis. Considering the toxicity and potentially environmental pollution of transition metals, the novel, efficient and convenient synthetic methodologies of 1,2,3-triazole under transition metal-free conditions have been received widely attention. Based on our work and research interesting, the aim of this review is to give an overview of the progress on the diverse synthetic methodologies of 1,2,3-triazole with transition metal-free since 2010.
2016, 36(8): 1790-1796
doi: 10.6023/cjoc201601037
Abstract:
As a special synthons containing C—N bond, hydrazine chemistry has attracted a growing interest of chemists due to its versatility in cross-coupling arylation. This review summarizes the recent advances in the coupling reactions of arylhydrazine, which is utilized as an effective arylation reagent in radical reactions, and transition metal-catalyzed homocoupling, Suzuki coupling and Heck coupling via C—N bond cleavage.
As a special synthons containing C—N bond, hydrazine chemistry has attracted a growing interest of chemists due to its versatility in cross-coupling arylation. This review summarizes the recent advances in the coupling reactions of arylhydrazine, which is utilized as an effective arylation reagent in radical reactions, and transition metal-catalyzed homocoupling, Suzuki coupling and Heck coupling via C—N bond cleavage.
2016, 36(8): 1797-1804
doi: 10.6023/cjoc201603010
Abstract:
Palladium-catalyzed oxidative functionalization of alkenes is one of the most powerful tools to synthesize complicated molecules. The related asymmetric reactions have received much attention. Due to the oxidative condition, however, compatible chiral ligand is quite limited. Recently, oxazoline-type ligand was applied in these reactions and exhibited good to excellent enantioselectivity. In this review, the recent studies on palladium-catalyzed asymmetric oxidative functionalization of alkenes with oxazoline ligands were summarized.
Palladium-catalyzed oxidative functionalization of alkenes is one of the most powerful tools to synthesize complicated molecules. The related asymmetric reactions have received much attention. Due to the oxidative condition, however, compatible chiral ligand is quite limited. Recently, oxazoline-type ligand was applied in these reactions and exhibited good to excellent enantioselectivity. In this review, the recent studies on palladium-catalyzed asymmetric oxidative functionalization of alkenes with oxazoline ligands were summarized.
2016, 36(8): 1805-1813
doi: 10.6023/cjoc201602018
Abstract:
Chiral phosphines are very useful in the fields of asymmetric catalysis, pharmaceutical chemistry, and materials. These compounds have been used as ligands coordinated to transition metals or organocatalysts in various reactions to furnish optically active products with high efficiency. Asymmetric phosphorus-addition reaction can be utilized for the direct preparation of chiral phosphorus compounds. This review summarizes the recent progress in the field of enantioselective phosphorus-addition reactions. Several examples of transition metal- and organocatalyst-promoted asymmetric hydrophosphination reactions of electron-deficient alkenes have been introduced.
Chiral phosphines are very useful in the fields of asymmetric catalysis, pharmaceutical chemistry, and materials. These compounds have been used as ligands coordinated to transition metals or organocatalysts in various reactions to furnish optically active products with high efficiency. Asymmetric phosphorus-addition reaction can be utilized for the direct preparation of chiral phosphorus compounds. This review summarizes the recent progress in the field of enantioselective phosphorus-addition reactions. Several examples of transition metal- and organocatalyst-promoted asymmetric hydrophosphination reactions of electron-deficient alkenes have been introduced.
2016, 36(8): 1814-1823
doi: 10.6023/cjoc201602021
Abstract:
Recently, the aromatic heterocyclic sulfide was widely used in medical and functional materials as an intermediate in organic chemistry and a structural unit in drug synthesis. Their synthetic method has become one of the hot research areas. This review summarizes the recent synthetic methods of aromatic heterocyclic thioether, which mainly involves metallic catalyzed and no metal-catalyzed methods, as well as benzene alkyne intermediate method. Some of their synthetic mechanisms were illustrated.
Recently, the aromatic heterocyclic sulfide was widely used in medical and functional materials as an intermediate in organic chemistry and a structural unit in drug synthesis. Their synthetic method has become one of the hot research areas. This review summarizes the recent synthetic methods of aromatic heterocyclic thioether, which mainly involves metallic catalyzed and no metal-catalyzed methods, as well as benzene alkyne intermediate method. Some of their synthetic mechanisms were illustrated.
2016, 36(8): 1824-1838
doi: 10.6023/cjoc201603014
Abstract:
The reduction of carbon dioxide, carboxylic acids and their derivatives is one of the fundamental transformations both in academia and industry. Considering the increasing environmental issues, the use of molecular hydrogen as the reducing agent is especially attractive. Due to the mild reaction condition, high reactivity and easy modification of homogeneous catalysis, the development of highly efficient and selective homogeneous hydrogenation catalysts to achieve the goal is becoming a hot topic. Impressive progresses have been made using homogenous catalysts derived from transition metals and various ligands as catalysts. Among them, the catalytic system combined with a transition metal and CH3C(CH2PPh2)3 (triphos) usually shows unique reactivity and selectivity. This review will summarize the advance in the hydrogenation of carbon dioxide, carboxylic acids and their derivatives using Ru/triphos, Co/triphos and Cu/triphos as catalysts, as well as their reaction mechanisms.
The reduction of carbon dioxide, carboxylic acids and their derivatives is one of the fundamental transformations both in academia and industry. Considering the increasing environmental issues, the use of molecular hydrogen as the reducing agent is especially attractive. Due to the mild reaction condition, high reactivity and easy modification of homogeneous catalysis, the development of highly efficient and selective homogeneous hydrogenation catalysts to achieve the goal is becoming a hot topic. Impressive progresses have been made using homogenous catalysts derived from transition metals and various ligands as catalysts. Among them, the catalytic system combined with a transition metal and CH3C(CH2PPh2)3 (triphos) usually shows unique reactivity and selectivity. This review will summarize the advance in the hydrogenation of carbon dioxide, carboxylic acids and their derivatives using Ru/triphos, Co/triphos and Cu/triphos as catalysts, as well as their reaction mechanisms.
2016, 36(8): 1839-1846
doi: 10.6023/cjoc201602035
Abstract:
Nine new N12-ethyl substituted indolocarbazole derivatives were synthesized. Their structures were identified by 1H NMR, 13C NMR and HRESIMS. The thiazolyl blue tetrazolium bromide (MTT) method was used to evaluate the cytotoxicities of these derivatives against A549, HepG-2 and Hela cell lines, while the cell counting kit-8 (CCK-8) method was used to evaluate cytotoxicity against K562 cell lines. The results showed that compounds 7～9 displayed comparable cytotoxicity to adriamycin (ADM) against K562 cell lines with the IC50 values of 0.43～0.93 μmol/L. Compounds 8 and 12 showed comparable cytotoxicity to ADM against Hela cell lines with the IC50 values of 1.23 and 0.43 μmol/L, respectively. The hydrochloride 14 of compound 13 exhibited good cytotoxicity against the four cell lines with the IC50 values of 0.23～1.72 μmol/L, indicating a worth of further study as an antitumor lead compound.
Nine new N12-ethyl substituted indolocarbazole derivatives were synthesized. Their structures were identified by 1H NMR, 13C NMR and HRESIMS. The thiazolyl blue tetrazolium bromide (MTT) method was used to evaluate the cytotoxicities of these derivatives against A549, HepG-2 and Hela cell lines, while the cell counting kit-8 (CCK-8) method was used to evaluate cytotoxicity against K562 cell lines. The results showed that compounds 7～9 displayed comparable cytotoxicity to adriamycin (ADM) against K562 cell lines with the IC50 values of 0.43～0.93 μmol/L. Compounds 8 and 12 showed comparable cytotoxicity to ADM against Hela cell lines with the IC50 values of 1.23 and 0.43 μmol/L, respectively. The hydrochloride 14 of compound 13 exhibited good cytotoxicity against the four cell lines with the IC50 values of 0.23～1.72 μmol/L, indicating a worth of further study as an antitumor lead compound.
2016, 36(8): 1847-1853
doi: 10.6023/cjoc201601021
Abstract:
A series of propargylic amines were synthesized from terminal alkynes, dichloromethane and organic amines by using waste crab shell powders supported-CuI (CSPs-CuI) as catalyst. Using waste crab shell powders as catalyst support, not only resolve the problem of environment pollution and resources waste, but also produce propargylic amines through a highly efficient and green method. CSPs-CuI was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TG) and atomic absorption spectroscopy (AAS). The reaction conditions were optimized by the investigation of catalyst support and base types. The propargyllic amines were obtained readily in intermediate to excellent yields under the optimal reaction condition. CSPs-CuI showed good reusability and could be recovered easily through filtration and washing. It was reused at least 4 times without obvious loss of catalytic performance.
A series of propargylic amines were synthesized from terminal alkynes, dichloromethane and organic amines by using waste crab shell powders supported-CuI (CSPs-CuI) as catalyst. Using waste crab shell powders as catalyst support, not only resolve the problem of environment pollution and resources waste, but also produce propargylic amines through a highly efficient and green method. CSPs-CuI was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TG) and atomic absorption spectroscopy (AAS). The reaction conditions were optimized by the investigation of catalyst support and base types. The propargyllic amines were obtained readily in intermediate to excellent yields under the optimal reaction condition. CSPs-CuI showed good reusability and could be recovered easily through filtration and washing. It was reused at least 4 times without obvious loss of catalytic performance.
2016, 36(8): 1854-1862
doi: 10.6023/cjoc201602030
Abstract:
Constitutive activation of signal transducer and activator of transcription 3 (STAT3) is involved in the occurrence and development of the tumors, and is regarded as an attractive therapeutic target for cancer therapy. Our laboratory discovered some STAT3 inhibitors containing benzothiazole scaffold through virtual screening before. In a continuing effort to develop more potential STAT3 inhibitors, twenty-one target compounds based on our identified hit compound (16v) were rational designed and synthesized. These structures were characterized by 1H NMR, 13C NMR and HRMS. All the target compounds were tested for their inhibitory activity using a STAT3 luciferase reporter system. The results showed that many compounds displayed better activity than lead compound 16v in series I. However, compounds containing thiazolo[5,4-d]pyrimidine scaffold led to the loss of inhibitory activity. This may attributed to the losing of hydrogen bonding to Glu638.
Constitutive activation of signal transducer and activator of transcription 3 (STAT3) is involved in the occurrence and development of the tumors, and is regarded as an attractive therapeutic target for cancer therapy. Our laboratory discovered some STAT3 inhibitors containing benzothiazole scaffold through virtual screening before. In a continuing effort to develop more potential STAT3 inhibitors, twenty-one target compounds based on our identified hit compound (16v) were rational designed and synthesized. These structures were characterized by 1H NMR, 13C NMR and HRMS. All the target compounds were tested for their inhibitory activity using a STAT3 luciferase reporter system. The results showed that many compounds displayed better activity than lead compound 16v in series I. However, compounds containing thiazolo[5,4-d]pyrimidine scaffold led to the loss of inhibitory activity. This may attributed to the losing of hydrogen bonding to Glu638.
2016, 36(8): 1863-1868
doi: 10.6023/cjoc201602019
Abstract:
By reacting calix[4]arene-1,3-bis-amino derivative 3 with pyromellitic dianhydride, 1,4,5,8-naphthalenetetracar- boxylic dianhydride and perylene-3,4,9,10-tetracarboxylic dianhydride, respectively, three novel biscalix[4]arene derivatives 4, 5 and 6 with large conjugated aromatic bridges were prepared in “2+2” mode in yields of 60%～70%. The liquid-liquid extraction experiments of compounds 4, 5 and 6 suggested that they possess excellent extraction abilities for orange I (OI) and victoria blue B (VB). The extraction percentage of compound 6 for OI is as high as 88.3%. The complexation titration UV-vis spectra, Job plot titration and the ESI-MS complexation spectrum implied the formation of 1:1 complexes in DMSO solution. The highest association constant is 2.80×105 L·mol-1 for compound 6 with OI. The complexation abilities of compounds 4, 5 and 6 exhibit the order of compound 4< compound 5< compound 6, indicating that the aromatic conjugate bridges in biscalix[4]arene play important role for the dye complexation.
By reacting calix[4]arene-1,3-bis-amino derivative 3 with pyromellitic dianhydride, 1,4,5,8-naphthalenetetracar- boxylic dianhydride and perylene-3,4,9,10-tetracarboxylic dianhydride, respectively, three novel biscalix[4]arene derivatives 4, 5 and 6 with large conjugated aromatic bridges were prepared in “2+2” mode in yields of 60%～70%. The liquid-liquid extraction experiments of compounds 4, 5 and 6 suggested that they possess excellent extraction abilities for orange I (OI) and victoria blue B (VB). The extraction percentage of compound 6 for OI is as high as 88.3%. The complexation titration UV-vis spectra, Job plot titration and the ESI-MS complexation spectrum implied the formation of 1:1 complexes in DMSO solution. The highest association constant is 2.80×105 L·mol-1 for compound 6 with OI. The complexation abilities of compounds 4, 5 and 6 exhibit the order of compound 4< compound 5< compound 6, indicating that the aromatic conjugate bridges in biscalix[4]arene play important role for the dye complexation.
2016, 36(8): 1869-1877
doi: 10.6023/cjoc201602027
Abstract:
Molecular-based magnetic material can be used for information storage, magnetic imaging, photo-magnetic switching and so on. So the design and synthesis of the molecular-based magnet is a focus of contemporary science research. Sparked by the strategy of molecular magnets, the novel photomodulation magnetic molecular-based magnet photochromic biindenylidenedione derivative with 2-nitropropane radical and 2,2,6,6-tetramethyl-piperidinyloxy (TEMPO) radical (4) was synthesized. The synthetic method of compound 4 is that starting from photochromic biindenylidenedione derivative 7,7'-dimethyl-[2,2'-bi-1H-indene]-3,3'-diethyl-3,3'-di-hydroxy-1,1'-dione (1), via bromination reaction, 7,7'-bis(bromomethyl)- [2,2'-bi-1H-indene]-3,3'-diethyl-3,3'-dihydroxy-1,1'-dione (2) was obtained. Sodium ethoxide, 2-nitropropane and compound 2 were dissolved in absolute ethanol reaction to obtain biindenylidenedione derivative with 2-nitropropane radical and formyl 3. The structure of compound 3 was confirmed by 1H NMR, MS and element analysis. The results indicated that 2-nitropropane group bonds with one methylene on the benzene ring of the compound 3. In further analysis to 1H NMR and electron spin-resonace (ESR) spectra of compound 3 demonstrated that single electron spin exists in 2-nitropropane group. On the basis compound 3, stable nitroxide radical TEMPO was successfully introduced into the benzene rings of photochromic biindeny lidenedione derivative to obtain compound 4. The properties of compounds 2, 3 and 4 were investigated. The testing results display that the solid compounds 2～4 possess photochromic property. ESR spectrum was found when irradiated solid compound 2. ESR spectrum was found and changed before and after photoirradiation in solid state of compound 3 and 4. The magnetic susceptibility measurement shows that the antiferromagnetic interaction for before and after photoirradiation in solid state of compound 4, and the antiferromagnetic interaction becomes stronger after photoirradiation. These testing results demonstrated that after photoirradiation in solid state of compound 3 and 4, there are two or three kinds of spin centres after photoirradiation: one is 2-nitropropane or TEMPO radical, and another is photo-generated radical of two indanione moieties. The color and magnetic of the solid compound 4 can be photomodulated.
Molecular-based magnetic material can be used for information storage, magnetic imaging, photo-magnetic switching and so on. So the design and synthesis of the molecular-based magnet is a focus of contemporary science research. Sparked by the strategy of molecular magnets, the novel photomodulation magnetic molecular-based magnet photochromic biindenylidenedione derivative with 2-nitropropane radical and 2,2,6,6-tetramethyl-piperidinyloxy (TEMPO) radical (4) was synthesized. The synthetic method of compound 4 is that starting from photochromic biindenylidenedione derivative 7,7'-dimethyl-[2,2'-bi-1H-indene]-3,3'-diethyl-3,3'-di-hydroxy-1,1'-dione (1), via bromination reaction, 7,7'-bis(bromomethyl)- [2,2'-bi-1H-indene]-3,3'-diethyl-3,3'-dihydroxy-1,1'-dione (2) was obtained. Sodium ethoxide, 2-nitropropane and compound 2 were dissolved in absolute ethanol reaction to obtain biindenylidenedione derivative with 2-nitropropane radical and formyl 3. The structure of compound 3 was confirmed by 1H NMR, MS and element analysis. The results indicated that 2-nitropropane group bonds with one methylene on the benzene ring of the compound 3. In further analysis to 1H NMR and electron spin-resonace (ESR) spectra of compound 3 demonstrated that single electron spin exists in 2-nitropropane group. On the basis compound 3, stable nitroxide radical TEMPO was successfully introduced into the benzene rings of photochromic biindeny lidenedione derivative to obtain compound 4. The properties of compounds 2, 3 and 4 were investigated. The testing results display that the solid compounds 2～4 possess photochromic property. ESR spectrum was found when irradiated solid compound 2. ESR spectrum was found and changed before and after photoirradiation in solid state of compound 3 and 4. The magnetic susceptibility measurement shows that the antiferromagnetic interaction for before and after photoirradiation in solid state of compound 4, and the antiferromagnetic interaction becomes stronger after photoirradiation. These testing results demonstrated that after photoirradiation in solid state of compound 3 and 4, there are two or three kinds of spin centres after photoirradiation: one is 2-nitropropane or TEMPO radical, and another is photo-generated radical of two indanione moieties. The color and magnetic of the solid compound 4 can be photomodulated.
2016, 36(8): 1878-1882
doi: 10.6023/cjoc201602028
Abstract:
In the synthesis of related substance E of tadalafil, a special intramolecular aldol-like reaction was discovered. In this reaction, the α-carbon of ketone attacks the carbonyl group of amide, forming a stable amino hemiketal structure. This reaction can only be realized under the catalysis of silica gel, and other acidic or basic reaction conditions are difficult to obtain the desired product. This finding is a meaningful supplement and extension to aldol reactions.
In the synthesis of related substance E of tadalafil, a special intramolecular aldol-like reaction was discovered. In this reaction, the α-carbon of ketone attacks the carbonyl group of amide, forming a stable amino hemiketal structure. This reaction can only be realized under the catalysis of silica gel, and other acidic or basic reaction conditions are difficult to obtain the desired product. This finding is a meaningful supplement and extension to aldol reactions.
2016, 36(8): 1883-1889
doi: 10.6023/cjoc201603021
Abstract:
In order to discover novel compounds with high-activity to control aphid, aphid alarm pheromone (E)-β-farnesene (EBF) was chosen as lead compound and a series of substituted EBF analogues were designed by replacing unstable conjugated double bond of EBF with different substitutions benzene ring. An N-alkylation route was optimized by using aniline and (E)-1-chloro-3,7-dimethyl-2,6-octadiene. Nineteen EBF analogues were synthesized with yields of 39%～83% in this optimization reaction condition. Their structures were confirmed by 1H NMR, 13C NMR and HRMS analysis. Bioassay showed that the title compounds demonstrated repellent activity against Myzus persicae (Sulzer). In particular, 4d, 4h and 4k exhibited excellent repellent activity of 56.3%, 58.3% and 50.3% respectively. The performed structure-activity relationship indicated that introduction of halogen group at the 4 position of phenyl ring displayed relatively higher activity.
In order to discover novel compounds with high-activity to control aphid, aphid alarm pheromone (E)-β-farnesene (EBF) was chosen as lead compound and a series of substituted EBF analogues were designed by replacing unstable conjugated double bond of EBF with different substitutions benzene ring. An N-alkylation route was optimized by using aniline and (E)-1-chloro-3,7-dimethyl-2,6-octadiene. Nineteen EBF analogues were synthesized with yields of 39%～83% in this optimization reaction condition. Their structures were confirmed by 1H NMR, 13C NMR and HRMS analysis. Bioassay showed that the title compounds demonstrated repellent activity against Myzus persicae (Sulzer). In particular, 4d, 4h and 4k exhibited excellent repellent activity of 56.3%, 58.3% and 50.3% respectively. The performed structure-activity relationship indicated that introduction of halogen group at the 4 position of phenyl ring displayed relatively higher activity.
2016, 36(8): 1890-1894
doi: 10.6023/cjoc201603020
Abstract:
This paper reports a simple method for the synthesis of α,β-unsaturated olefinic amides from β-keto amides in the presence of NaBH4 and alkali. However, this reaction only leads to quantitatively reduction product of carbonyl compounds in the presence of NaBH4 and FeCl3. The structures of products were confirmed by 1H NMR and 13C NMR spectra. In addition, a possible reaction mechanism was also proposed.
This paper reports a simple method for the synthesis of α,β-unsaturated olefinic amides from β-keto amides in the presence of NaBH4 and alkali. However, this reaction only leads to quantitatively reduction product of carbonyl compounds in the presence of NaBH4 and FeCl3. The structures of products were confirmed by 1H NMR and 13C NMR spectra. In addition, a possible reaction mechanism was also proposed.
2016, 36(8): 1895-1906
doi: 10.6023/cjoc201512049
Abstract:
Lewis base catalyzed enantioselective hydrosilylation of non-ortho-substituted N-aryl diaryl ketimines was realized. In the presence of 20 mol% of the optimal catalyst, the reactions provided a series of (diarylmethyl)amines with high yields (up to 97%) in moderate to good enantioselectivities (up to 89% ee). The absolute configuration of one product was determined by X-ray crystallographic analysis.
Lewis base catalyzed enantioselective hydrosilylation of non-ortho-substituted N-aryl diaryl ketimines was realized. In the presence of 20 mol% of the optimal catalyst, the reactions provided a series of (diarylmethyl)amines with high yields (up to 97%) in moderate to good enantioselectivities (up to 89% ee). The absolute configuration of one product was determined by X-ray crystallographic analysis.
2016, 36(8): 1907-1914
doi: 10.6023/cjoc201512022
Abstract:
Six amino-alcohol modified β-cyclodextrins CD-1～CD-6 were synthesized by nucleophilic substitution from mono(6-O-p-tolylsulfonyl)-β-cyclodextrin with the yields of 34%～58%, and were verified by 1H NMR, 13C NMR and ESI-MS techniques. These β-cyclodextrin derivatives were applied to the asymmetric epoxidation of trans-chalcone by H2O2. And the results implied that the dosage of the β-cyclodextrin derivatives and the structure of the modified group had an important effect on the enantioselectivity in the reaction. Among them, CD-1 exhibited the best performance in the asymmetric epoxidation of trans-chalcone employed H2O2 and NaHCO3 as oxidant, and 25.7% ee value was obtained. It were showed from the spectra of 2D-1H ROESY NMR that, CD-1 could form inclusion complex with trans-chalcone and self-inclusion existed in all the β-cyclodextrin derivatives CD-1～CD-6, which affected the enhancement of the ee value. And the two kinds of inclusion complexes were confirmed by quantum chemistry calculation too.
Six amino-alcohol modified β-cyclodextrins CD-1～CD-6 were synthesized by nucleophilic substitution from mono(6-O-p-tolylsulfonyl)-β-cyclodextrin with the yields of 34%～58%, and were verified by 1H NMR, 13C NMR and ESI-MS techniques. These β-cyclodextrin derivatives were applied to the asymmetric epoxidation of trans-chalcone by H2O2. And the results implied that the dosage of the β-cyclodextrin derivatives and the structure of the modified group had an important effect on the enantioselectivity in the reaction. Among them, CD-1 exhibited the best performance in the asymmetric epoxidation of trans-chalcone employed H2O2 and NaHCO3 as oxidant, and 25.7% ee value was obtained. It were showed from the spectra of 2D-1H ROESY NMR that, CD-1 could form inclusion complex with trans-chalcone and self-inclusion existed in all the β-cyclodextrin derivatives CD-1～CD-6, which affected the enhancement of the ee value. And the two kinds of inclusion complexes were confirmed by quantum chemistry calculation too.
2016, 36(8): 1915-1920
doi: 10.6023/cjoc201601040
Abstract:
The reaction of 5(R)-(l-menthoxy)-2(5H)-furanone and diethyl bromomalonate was investigated in the presence of anhydrous K2CO3 and phase transfer catalyst tetrabutylammonium bromide (TBAB) using CH3CN as solvent at 80 ℃. In the above condition, the expected novel chiral cyclopropane/butyrolactone derivative 3 with two ethyl ester groups was obtained, and at the same time, another chiral cycloproane/butyrolactone 5 bearing only one ethyl ester group, and trace amount of bromo-substitued compound 6 were also obtained. The possible mechanism was proposed based on the analysis of the products.
The reaction of 5(R)-(l-menthoxy)-2(5H)-furanone and diethyl bromomalonate was investigated in the presence of anhydrous K2CO3 and phase transfer catalyst tetrabutylammonium bromide (TBAB) using CH3CN as solvent at 80 ℃. In the above condition, the expected novel chiral cyclopropane/butyrolactone derivative 3 with two ethyl ester groups was obtained, and at the same time, another chiral cycloproane/butyrolactone 5 bearing only one ethyl ester group, and trace amount of bromo-substitued compound 6 were also obtained. The possible mechanism was proposed based on the analysis of the products.
2016, 36(8): 1921-1925
doi: 10.6023/cjoc201602012
Abstract:
In order to develop the anti-tumor agents with high efficiency and low toxicity, a series of novel azasugar modified anthraquinone derivatives have been designed and synthesized by the ammonolysis of N-alkylamino azasugar with rhine and microwave assisted Ullmann coupling reaction of N-alkylamino azasugar with 1-amino-4-bromoanthraquinone-2-sulfonic acid. Their cytotoxic activities against Hela, A549, MCF-7 and MGC-803 cells were preliminarily evaluated.
In order to develop the anti-tumor agents with high efficiency and low toxicity, a series of novel azasugar modified anthraquinone derivatives have been designed and synthesized by the ammonolysis of N-alkylamino azasugar with rhine and microwave assisted Ullmann coupling reaction of N-alkylamino azasugar with 1-amino-4-bromoanthraquinone-2-sulfonic acid. Their cytotoxic activities against Hela, A549, MCF-7 and MGC-803 cells were preliminarily evaluated.
2016, 36(8): 1926-1931
doi: 10.6023/cjoc201603003
Abstract:
In the presence of iodobenzene diacetate (PhI(OAc)2), a new CuBr catalyzed coupling reaction of alkynes and amines for the synthesis of propargyl amines was developed. When terminal alkynes, PhI(OAc)2, and amines were reacted in CH3CN at 70 ℃ for 3 h under N2 atmosphere and in the presence of CuBr, the desired propargyl amines were obtained in good yields. Furthermore, no matter aromatic or aliphatic alkynes, were all found to tolerate the reaction conditions. To the best of our knowledge, it is the first time that PhI(OAc)2 has been used for the synthesis of propargyl amines in one-pot operation from alkynes and amines.
In the presence of iodobenzene diacetate (PhI(OAc)2), a new CuBr catalyzed coupling reaction of alkynes and amines for the synthesis of propargyl amines was developed. When terminal alkynes, PhI(OAc)2, and amines were reacted in CH3CN at 70 ℃ for 3 h under N2 atmosphere and in the presence of CuBr, the desired propargyl amines were obtained in good yields. Furthermore, no matter aromatic or aliphatic alkynes, were all found to tolerate the reaction conditions. To the best of our knowledge, it is the first time that PhI(OAc)2 has been used for the synthesis of propargyl amines in one-pot operation from alkynes and amines.
2016, 36(8): 1932-1936
doi: 10.6023/cjoc201602001
Abstract:
In this paper, a series of 13-aryl-6,13-dihydro-3H-quino[4,3-b]pyrrolo[3,2-f]quinolin-12(11H)-one derivatives was synthesized in EtOH under catalyst-free conditions using aromatic aldehydes, 5-aminoindole and 4-hydroxyquinolin-2(1H)-one as reactants. The structure of 4b was confirmed by X-ray diffraction analysis. This procedure has the advantages of simplicity and easy operation. An efficient method for the synthesis of fused pentacyclic heterocycles containing biquinolines moieties is provided.
In this paper, a series of 13-aryl-6,13-dihydro-3H-quino[4,3-b]pyrrolo[3,2-f]quinolin-12(11H)-one derivatives was synthesized in EtOH under catalyst-free conditions using aromatic aldehydes, 5-aminoindole and 4-hydroxyquinolin-2(1H)-one as reactants. The structure of 4b was confirmed by X-ray diffraction analysis. This procedure has the advantages of simplicity and easy operation. An efficient method for the synthesis of fused pentacyclic heterocycles containing biquinolines moieties is provided.
2016, 36(8): 1937-1941
doi: 10.6023/cjoc201603024
Abstract:
The complexation between the novel water-soluble cylindrical macrotricyclic host and paraquat guests in both solution and solid state was investigated in detail. It was found that the host could form 1:1 complexes with paraquat salts in water solution and solid state. Interestingly, the complexation and decomplexation of the complexes between the host and the guest could be achieved by changing the pH of the solution, and the process could also be observed by naked eye.
The complexation between the novel water-soluble cylindrical macrotricyclic host and paraquat guests in both solution and solid state was investigated in detail. It was found that the host could form 1:1 complexes with paraquat salts in water solution and solid state. Interestingly, the complexation and decomplexation of the complexes between the host and the guest could be achieved by changing the pH of the solution, and the process could also be observed by naked eye.
2016, 36(8): 1942-1947
doi: 10.6023/cjoc201601014
Abstract:
A new simple and efficient one-pot synthesis of thiazolidinone derivatives via aldehydes, amines and mercaptoacetic acid in the presence of Zn(OAc)2-Schiff base complex immobilized on MCM-41 is described. A variety of aldehydes and amines were engaged in the study and afforded respective thiazolidinones in high yield (up to 98%). Moreover, consistent activity of recovered catalyst was found to be almost same up to five cycles in 80% yield.
A new simple and efficient one-pot synthesis of thiazolidinone derivatives via aldehydes, amines and mercaptoacetic acid in the presence of Zn(OAc)2-Schiff base complex immobilized on MCM-41 is described. A variety of aldehydes and amines were engaged in the study and afforded respective thiazolidinones in high yield (up to 98%). Moreover, consistent activity of recovered catalyst was found to be almost same up to five cycles in 80% yield.
2016, 36(8): 1948-1953
doi: 10.6023/cjoc201601032
Abstract:
Twelve kinds of diphenyl-2,4-dioxa-8,10-diazaspiro[5.5]undecane-1,5,9-trione derivatives were synthesized by the three-component one-pot reaction of aromatic aldehydes with urea and 2,2-butylidene-1,3-dioxane-4,6-dione or 2,2-pentyli- dene-1,3-dioxane-4,6-dione under solvent-free and catalyst-free. The yields ranged from 49% to 63%. Its advantages were no solvent pollution and mild reaction conditions. Furthermore, a proposed reaction mechanism for this condensation reaction was speculated and the relationship between reaction speed and substituent groups was also described. All the compounds synthesized were confirmed by 1H NMR, 13C NMR, ESI-MS and IR techniques.
Twelve kinds of diphenyl-2,4-dioxa-8,10-diazaspiro[5.5]undecane-1,5,9-trione derivatives were synthesized by the three-component one-pot reaction of aromatic aldehydes with urea and 2,2-butylidene-1,3-dioxane-4,6-dione or 2,2-pentyli- dene-1,3-dioxane-4,6-dione under solvent-free and catalyst-free. The yields ranged from 49% to 63%. Its advantages were no solvent pollution and mild reaction conditions. Furthermore, a proposed reaction mechanism for this condensation reaction was speculated and the relationship between reaction speed and substituent groups was also described. All the compounds synthesized were confirmed by 1H NMR, 13C NMR, ESI-MS and IR techniques.
2016, 36(8): 1954-1957
doi: 10.6023/cjoc201601033
Abstract:
With N-chlorosuccinimide as the chlorinating source, the dichlorination of isonitriles has been achieved to afford N-phenyldichloroimide compounds under mild and convenient conditions. The optimized reaction conditions were established through systematic investigations of the effect of solvents, temperature, time, chlorinating sources and their dosages in the reaction. The reaction exhibits good compatibility of various substrates, and a variety of isonitriles with different substituted patterns can undergo the dichlorination smoothly and furnish products with high yields of up to 93%.
With N-chlorosuccinimide as the chlorinating source, the dichlorination of isonitriles has been achieved to afford N-phenyldichloroimide compounds under mild and convenient conditions. The optimized reaction conditions were established through systematic investigations of the effect of solvents, temperature, time, chlorinating sources and their dosages in the reaction. The reaction exhibits good compatibility of various substrates, and a variety of isonitriles with different substituted patterns can undergo the dichlorination smoothly and furnish products with high yields of up to 93%.
2016, 36(8): 1958-1962
doi: 10.6023/cjoc201601046
Abstract:
A conversion of aromatic aldehydes to dichloromethylated or trichloromethylated aromatics has been firstly accomplished by using phosphorus pentachloride as the chlorination agent. In this reaction, dichloromethylated aromatics can be obtained alone when it keeps constantly blowing oxygen into the reaction solution, and 2-methylpropionitrule can also be used to promote the formation of trichloromethylated aromatics. And it has provided a new method of highly efficient synthesis for dichloromethylated aromatics and trichloromethylated aromatics in good yields.
A conversion of aromatic aldehydes to dichloromethylated or trichloromethylated aromatics has been firstly accomplished by using phosphorus pentachloride as the chlorination agent. In this reaction, dichloromethylated aromatics can be obtained alone when it keeps constantly blowing oxygen into the reaction solution, and 2-methylpropionitrule can also be used to promote the formation of trichloromethylated aromatics. And it has provided a new method of highly efficient synthesis for dichloromethylated aromatics and trichloromethylated aromatics in good yields.
2016, 36(8): 1963-1969
doi: 10.6023/cjoc201512046
Abstract:
Poly(vinyl chloride) (PVC)-based light stabilizer was prepared by introducing the lower molecular UV absorbents into PVC using quantitative click reaction, which could avoid some defects (low permanence of light aging resistance property and environmental pollution) caused by poor polymer compatability of low molecular UV absorbent. Azide groups were firstly introduced into the backbone of PVC via a nucleophilic reaction to obtain PVC-N3 with different substitutive rate, and 2,4-dihydroxy-benzophenone (2,4-DHBP) was treated with propargyl bromide to prepare alkynyl-containing 2-hydroxy-4- (prop-2-ynyloxy)benzophenone (2,4-DHBP-P). Then, copper-catalyzed Husigen-Click cycloaddition reaction was performed between the pendant azide groups of PVC-N3 and alkynyl of 2,4-DHBP-P to afford the desired PVC-based UV absorbents (2,4-DHBP-PVC) with different amounts of benzophenone moieties. These 2,4-DHBP-PVC showed great resistance to photoaging while exposed to UV irradiation. Their ratio of carbonyl to methylene group were far lower than that of pure PVC (0.3331) after UV irradiating for 200 h, and the minimum value is about 0.03998.
Poly(vinyl chloride) (PVC)-based light stabilizer was prepared by introducing the lower molecular UV absorbents into PVC using quantitative click reaction, which could avoid some defects (low permanence of light aging resistance property and environmental pollution) caused by poor polymer compatability of low molecular UV absorbent. Azide groups were firstly introduced into the backbone of PVC via a nucleophilic reaction to obtain PVC-N3 with different substitutive rate, and 2,4-dihydroxy-benzophenone (2,4-DHBP) was treated with propargyl bromide to prepare alkynyl-containing 2-hydroxy-4- (prop-2-ynyloxy)benzophenone (2,4-DHBP-P). Then, copper-catalyzed Husigen-Click cycloaddition reaction was performed between the pendant azide groups of PVC-N3 and alkynyl of 2,4-DHBP-P to afford the desired PVC-based UV absorbents (2,4-DHBP-PVC) with different amounts of benzophenone moieties. These 2,4-DHBP-PVC showed great resistance to photoaging while exposed to UV irradiation. Their ratio of carbonyl to methylene group were far lower than that of pure PVC (0.3331) after UV irradiating for 200 h, and the minimum value is about 0.03998.
