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2016 Volume 36 Issue 7
2016, 36(7): 1447-1464
doi: 10.6023/cjoc201603030
Abstract:
Leuconolam-leuconoxine-mersicarpine monoterpene indole alkaloids are mainly isolated from Apocynaceae Kopsia species of plant. Though sharing the same biogenetic origin, they are a family of natural products showing incredible structural complexity and diversity. Moreover, many of them exhibit excellent bioactivities, for example, anti-inflammatory, anti-tumor activities. The progress in the total synthesis of this remarkable family of alkaloids is reviewed.
Leuconolam-leuconoxine-mersicarpine monoterpene indole alkaloids are mainly isolated from Apocynaceae Kopsia species of plant. Though sharing the same biogenetic origin, they are a family of natural products showing incredible structural complexity and diversity. Moreover, many of them exhibit excellent bioactivities, for example, anti-inflammatory, anti-tumor activities. The progress in the total synthesis of this remarkable family of alkaloids is reviewed.
2016, 36(7): 1465-1483
doi: 10.6023/cjoc201601007
Abstract:
In recent years, metal and their complexes-catalyzed organic reactions have received much attention in organic chemistry due to their rapidity and efficiency. Iron complexes have attracted much attention from chemical society due to the advantages of high catalytic activity and selectivity. The advances of iron complexes-catalyzed organic reactions are reviewed, such as polymerisation reactions, hydrosilylation/hydroboration, cycloaddition, redox reactions, cross-coupling reactions and 1,4-additions, and the prospects of its development are forecasted.
In recent years, metal and their complexes-catalyzed organic reactions have received much attention in organic chemistry due to their rapidity and efficiency. Iron complexes have attracted much attention from chemical society due to the advantages of high catalytic activity and selectivity. The advances of iron complexes-catalyzed organic reactions are reviewed, such as polymerisation reactions, hydrosilylation/hydroboration, cycloaddition, redox reactions, cross-coupling reactions and 1,4-additions, and the prospects of its development are forecasted.
2016, 36(7): 1484-1500
doi: 10.6023/cjoc201601022
Abstract:
The supported N-heterocyclic carbene (NHC) catalysts have been extensively applied in the catalysis of different organic reactions due to its unique characteristic such as high reactivity, easy separation, purification and recyclability. In this paper, the recent progresses in synthesis and application of supported N-heterocyclic carbene metal complexes based on various types of supports, such as polymer, magnetic nanoparticles, carbon and silica material have been reviewed.
The supported N-heterocyclic carbene (NHC) catalysts have been extensively applied in the catalysis of different organic reactions due to its unique characteristic such as high reactivity, easy separation, purification and recyclability. In this paper, the recent progresses in synthesis and application of supported N-heterocyclic carbene metal complexes based on various types of supports, such as polymer, magnetic nanoparticles, carbon and silica material have been reviewed.
2016, 36(7): 1501-1512
doi: 10.6023/cjoc201601027
Abstract:
Diels-Alder reaction is a [4+2] concerted cycloaddition reaction, which has attracted considerable attention since its discovery. Asymmetric Diels-Alder reaction is an effective method for synthesis of chiral intermediates, so it was widely applied in the total synthesis of drugs and natural products. α,β-Unsaturated carbonyl compounds are a kind of highly reactive versatile intermediates in organic synthesis, according to its structural characteristics and catalytic types, recent advances in asymmetric normal electron-demand Diels-Alder reaction of α,β-unsaturated carbonyl compounds are reviewed in this paper.
Diels-Alder reaction is a [4+2] concerted cycloaddition reaction, which has attracted considerable attention since its discovery. Asymmetric Diels-Alder reaction is an effective method for synthesis of chiral intermediates, so it was widely applied in the total synthesis of drugs and natural products. α,β-Unsaturated carbonyl compounds are a kind of highly reactive versatile intermediates in organic synthesis, according to its structural characteristics and catalytic types, recent advances in asymmetric normal electron-demand Diels-Alder reaction of α,β-unsaturated carbonyl compounds are reviewed in this paper.
2016, 36(7): 1513-1527
doi: 10.6023/cjoc201601028
Abstract:
Metal organic frameworks (MOFs) as a new type of organic/inorganic hybrid materials have attracted great focus of scientists in almost twenty years. It is composed of organic ligands and inorganic metal units and generally has a varied topological structure and unique physical/chemical properties. Due to its porous frame structure, large specific surface area and great variety, MOFs are widely used in functional materials, gas adsorption, drug sustained release, catalysis and organic synthesis. It can choose different ligands and metal ions, or change the strategy of synthesis to adjust the size, shape and structure of porous structure. The different ligands can determine the different structure and then affect the properties of MOFs. In this review, the preparation of particular functional MOFs structure and the application of various MOFs in organic synthesis and catalytic organic reactions are reviewed in detail. The summary and prospects about MOFs catalyzed organic reactions and the applications are proposed.
Metal organic frameworks (MOFs) as a new type of organic/inorganic hybrid materials have attracted great focus of scientists in almost twenty years. It is composed of organic ligands and inorganic metal units and generally has a varied topological structure and unique physical/chemical properties. Due to its porous frame structure, large specific surface area and great variety, MOFs are widely used in functional materials, gas adsorption, drug sustained release, catalysis and organic synthesis. It can choose different ligands and metal ions, or change the strategy of synthesis to adjust the size, shape and structure of porous structure. The different ligands can determine the different structure and then affect the properties of MOFs. In this review, the preparation of particular functional MOFs structure and the application of various MOFs in organic synthesis and catalytic organic reactions are reviewed in detail. The summary and prospects about MOFs catalyzed organic reactions and the applications are proposed.
2016, 36(7): 1528-1538
doi: 10.6023/cjoc201602011
Abstract:
The study of poly-nitro furazans in the field of energetic materials is very active, and many great advances have been made. According to other achievements in recent years, classified as single furazans, double furazans and other furazans by molecular structure, a large amount of poly-nitro furazans are summarized for the advances in certain aspect of synthesis. The properties and main applications of some important compounds are also introduced briefly.
The study of poly-nitro furazans in the field of energetic materials is very active, and many great advances have been made. According to other achievements in recent years, classified as single furazans, double furazans and other furazans by molecular structure, a large amount of poly-nitro furazans are summarized for the advances in certain aspect of synthesis. The properties and main applications of some important compounds are also introduced briefly.
2016, 36(7): 1539-1554
doi: 10.6023/cjoc201511038
Abstract:
Hypochlorous acid (HClO) is one of the biologically important reactive oxygen species (ROS), which plays important roles in the human immune defence system, and contributes to the destruction of invading bacteria and pathogens. But excessive formation of HClO can lead to tissue damage and a series of human diseases, such as atherosclerosis, arthritis and even cancers, etc. Therefore, a rapid, sensitive, and selective detection of HClO in biological samples is important. In recent years, fluorescent probes for HClO have been developed due to various advantages such as simplicity of operation, lower limit of detection, low toxicity, high sensitivity and selectivity. A general overview of the recent research on the design, synthesis and application of fluorescent probes for hypochlorous acid is provided.
Hypochlorous acid (HClO) is one of the biologically important reactive oxygen species (ROS), which plays important roles in the human immune defence system, and contributes to the destruction of invading bacteria and pathogens. But excessive formation of HClO can lead to tissue damage and a series of human diseases, such as atherosclerosis, arthritis and even cancers, etc. Therefore, a rapid, sensitive, and selective detection of HClO in biological samples is important. In recent years, fluorescent probes for HClO have been developed due to various advantages such as simplicity of operation, lower limit of detection, low toxicity, high sensitivity and selectivity. A general overview of the recent research on the design, synthesis and application of fluorescent probes for hypochlorous acid is provided.
2016, 36(7): 1555-1563
doi: 10.6023/cjoc201601042
Abstract:
Carbenes are very useful key intermediates in organic synthesis, which generally display high reactivity in chemical transformations. Metallocarbenes can be regarded as metal stabilized organic carbenes. The research progress of the metallocarbene formation and the related reactions based on triazole compounds are reviewed in this work. The RhII-catalyzed metallocarbenes derived from N-sulfonyl-1,2,3-triazoles, as well as the subsequent insertion reactions into other reaction systems to generate new C-C or C-hetero bonds, are specially focused.
Carbenes are very useful key intermediates in organic synthesis, which generally display high reactivity in chemical transformations. Metallocarbenes can be regarded as metal stabilized organic carbenes. The research progress of the metallocarbene formation and the related reactions based on triazole compounds are reviewed in this work. The RhII-catalyzed metallocarbenes derived from N-sulfonyl-1,2,3-triazoles, as well as the subsequent insertion reactions into other reaction systems to generate new C-C or C-hetero bonds, are specially focused.
2016, 36(7): 1564-1571
doi: 10.6023/cjoc201601012
Abstract:
Visible light mediated coupling reaction has obtained the widespread attention in recent years, and has been a most efficient method for building new C—C and C—X bonds. The development of visible light catalytic system also has provided a new means for decarboxylation reaction. Lots of studies on visible light catalytic decarboxylation reaction were published recently. In this paper, the visible light mediated decarboxylation reactions in recent years are briefly reviewed.
Visible light mediated coupling reaction has obtained the widespread attention in recent years, and has been a most efficient method for building new C—C and C—X bonds. The development of visible light catalytic system also has provided a new means for decarboxylation reaction. Lots of studies on visible light catalytic decarboxylation reaction were published recently. In this paper, the visible light mediated decarboxylation reactions in recent years are briefly reviewed.
2016, 36(7): 1572-1579
doi: 10.6023/cjoc201605006
Abstract:
Chiral cyclohexane motif is widespread in the molecular structures of nature products and medicinal chemicals. And polysubstituted chiral cyclohexanes are important building blocks in organic synthesis. A tandem cyclization via asymmetric induction for the construction of polysubstituted chiral cyclohexane skeletons is described. In the presence of phase-transfer-catalyst, optically active γ-nitro ketone reacted with chalcone smoothly to afford cyclohexane skeletons bearing five consecutive stereocenters in 40%~71% yields with 90%~98% ee. It should be noted that the scope of chalcone is broad. Especially, the asymmetric induction is kept at a high level in each step of the tandem cyclization reaction.
Chiral cyclohexane motif is widespread in the molecular structures of nature products and medicinal chemicals. And polysubstituted chiral cyclohexanes are important building blocks in organic synthesis. A tandem cyclization via asymmetric induction for the construction of polysubstituted chiral cyclohexane skeletons is described. In the presence of phase-transfer-catalyst, optically active γ-nitro ketone reacted with chalcone smoothly to afford cyclohexane skeletons bearing five consecutive stereocenters in 40%~71% yields with 90%~98% ee. It should be noted that the scope of chalcone is broad. Especially, the asymmetric induction is kept at a high level in each step of the tandem cyclization reaction.
2016, 36(7): 1580-1585
doi: 10.6023/cjoc201604049
Abstract:
A kind of fluorescence aromatic amide oligomer which based on 2,7-anthradiamine and 4,6-dihydroxyisophthalic acid derivatives is designed and synthesized. Tetraoxatridecanyl groups were introduced into the oligomers to improve their solubility in polar solvent. These structures were characterized by 1H NMR and HRMS. Fluorescence titration experiments indicated that A2 recognized 1,3,5-benzene-tricarboxylate ion by host-guest interaction. The apparent binding constant of the complex was measured to be about 1.95×103 L·mol-1, which opened a door on explore the supramolecular host-guest system by the track of fluorescence.
A kind of fluorescence aromatic amide oligomer which based on 2,7-anthradiamine and 4,6-dihydroxyisophthalic acid derivatives is designed and synthesized. Tetraoxatridecanyl groups were introduced into the oligomers to improve their solubility in polar solvent. These structures were characterized by 1H NMR and HRMS. Fluorescence titration experiments indicated that A2 recognized 1,3,5-benzene-tricarboxylate ion by host-guest interaction. The apparent binding constant of the complex was measured to be about 1.95×103 L·mol-1, which opened a door on explore the supramolecular host-guest system by the track of fluorescence.
2016, 36(7): 1586-1595
doi: 10.6023/cjoc201603039
Abstract:
Conjugated extension of an organic optoelectronic moiety along different directions is of significance for exploring its usage in material design and understanding its structure-property relationships. In this work, three benzo[1,2-b:4,5-b']di- thiophene-cored molecules were designed and synthesized by attaching donor-acceptor conjugated arms composed of thiophene and benzothiadiazole via the direction of its 2,6-position (horizontal), 4,8-position (vertical), and the both (cross), respectively. Compared with vertical linkage, the horizontal modification benefits the achievement of a red-shifted and wider absorption spectrum, a narrow bandgap and a more regular crystalline property, but a higher highest occupied molecular orbital (HOMO) energy level. Cross-shaped compound exhibits both a wide absorption spectrum and large absorption coefficients, and thus gave the largest short-circuit current density for its solar cell among three so-prepared devices.
Conjugated extension of an organic optoelectronic moiety along different directions is of significance for exploring its usage in material design and understanding its structure-property relationships. In this work, three benzo[1,2-b:4,5-b']di- thiophene-cored molecules were designed and synthesized by attaching donor-acceptor conjugated arms composed of thiophene and benzothiadiazole via the direction of its 2,6-position (horizontal), 4,8-position (vertical), and the both (cross), respectively. Compared with vertical linkage, the horizontal modification benefits the achievement of a red-shifted and wider absorption spectrum, a narrow bandgap and a more regular crystalline property, but a higher highest occupied molecular orbital (HOMO) energy level. Cross-shaped compound exhibits both a wide absorption spectrum and large absorption coefficients, and thus gave the largest short-circuit current density for its solar cell among three so-prepared devices.
2016, 36(7): 1596-1601
doi: 10.6023/cjoc201601019
Abstract:
The α-aminoxylation between α-azoleketones and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) was studied in this paper. Taking Cu(Ⅱ) salts as catalyst and air as oxidant, a number of alkoxyamines have been synthesized via α-aminoxylation between α-azoleketones and TEMPO in good yields at room temperature. This strategy is highlighted by appealing features such as mild reaction condition, inexpensive catalyst, green oxidant and good yield.
The α-aminoxylation between α-azoleketones and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) was studied in this paper. Taking Cu(Ⅱ) salts as catalyst and air as oxidant, a number of alkoxyamines have been synthesized via α-aminoxylation between α-azoleketones and TEMPO in good yields at room temperature. This strategy is highlighted by appealing features such as mild reaction condition, inexpensive catalyst, green oxidant and good yield.
2016, 36(7): 1602-1610
doi: 10.6023/cjoc201512031
Abstract:
Some B-norcholesteryl thiazole compounds were synthesized and their structures were determined by IR, NMR and HRMS. The antiproliferative activity of the compounds against human lung carcinoma (A549), cervical carcinoma (HeLa), liver carcinoma (HEPG2) and normal kidney epithelial (HEK293T) cells was assayed. The results showed that some compounds with a structure of N-methylthiazole showed distinct antiproliferative activity against A549 and HEPG2 cells. The compounds with a structure of N-phenylthiazole displayed a selective antiproliferative activity against HeLa cells and were almost inactive to HEK293T cells. The research provided a theoretical reference for the exploration of new anti-cancer agents.
Some B-norcholesteryl thiazole compounds were synthesized and their structures were determined by IR, NMR and HRMS. The antiproliferative activity of the compounds against human lung carcinoma (A549), cervical carcinoma (HeLa), liver carcinoma (HEPG2) and normal kidney epithelial (HEK293T) cells was assayed. The results showed that some compounds with a structure of N-methylthiazole showed distinct antiproliferative activity against A549 and HEPG2 cells. The compounds with a structure of N-phenylthiazole displayed a selective antiproliferative activity against HeLa cells and were almost inactive to HEK293T cells. The research provided a theoretical reference for the exploration of new anti-cancer agents.
2016, 36(7): 1611-1616
doi: 10.6023/cjoc201512042
Abstract:
1-Methyl-3-propyl-4-aminopyrazole-5-carbonitrile was synthesized by using 1-methyl-3-propylpyrazole-5-formic as starting materials in four steps reaction including acylation, dehydration, nitrification and reduction. Then pyrazolopyrimidinone derivatives were obtained from the condensation of 1-methyl-3-propyl-4-aminopyrazole-5-carbonitrile and aldehydes. 1-Methyl-3-propyl-4-nitropyrazole-5-carbonitrile was reduced to amine in the presence of palladium-charcoal. Three intermediate products, hydroxylamine, azoxypyrazole and azopyrazole, were separated and detected with HPLC and HPLC-HRMS during the formation of amine pyrazole. Possible reduction mechanism was proposed. The structures of products were characterized by 1H NMR, 13C NMR, IR spectra and MS.
1-Methyl-3-propyl-4-aminopyrazole-5-carbonitrile was synthesized by using 1-methyl-3-propylpyrazole-5-formic as starting materials in four steps reaction including acylation, dehydration, nitrification and reduction. Then pyrazolopyrimidinone derivatives were obtained from the condensation of 1-methyl-3-propyl-4-aminopyrazole-5-carbonitrile and aldehydes. 1-Methyl-3-propyl-4-nitropyrazole-5-carbonitrile was reduced to amine in the presence of palladium-charcoal. Three intermediate products, hydroxylamine, azoxypyrazole and azopyrazole, were separated and detected with HPLC and HPLC-HRMS during the formation of amine pyrazole. Possible reduction mechanism was proposed. The structures of products were characterized by 1H NMR, 13C NMR, IR spectra and MS.
2016, 36(7): 1617-1625
doi: 10.6023/cjoc201512051
Abstract:
To improve the concentration in liver lesion tissue and increase the anti-hepatitis B virus (HBV) activities of Matijin-Su (MTS) derivatives, five hepatic targeting galactopyranosyl derivatives of MTS were synthesized by indirect connecting the liver targeting galactose ligands to MTS using ethanolamin as a linker and their structures were confirmed by 1H NMR, 13CNMR, 1H-1H COSY, HMQC and ESI-MS. The anti-HBV activities of those compounds were evaluated in HepG2 2.2.15 cells. The screening results showed that all target compounds had inhibitory effect on HBV DNA replication in HepG2 2.2.15 cells in a dose-response manner.
To improve the concentration in liver lesion tissue and increase the anti-hepatitis B virus (HBV) activities of Matijin-Su (MTS) derivatives, five hepatic targeting galactopyranosyl derivatives of MTS were synthesized by indirect connecting the liver targeting galactose ligands to MTS using ethanolamin as a linker and their structures were confirmed by 1H NMR, 13CNMR, 1H-1H COSY, HMQC and ESI-MS. The anti-HBV activities of those compounds were evaluated in HepG2 2.2.15 cells. The screening results showed that all target compounds had inhibitory effect on HBV DNA replication in HepG2 2.2.15 cells in a dose-response manner.
2016, 36(7): 1626-1635
doi: 10.6023/cjoc201602004
Abstract:
With the aim of obtaining potential antitumor candidates with more efficiency and more economic value. A series of 3,6-substituted-1,2,4-triazolo[3,4-a]phthalazine derivatives were synthesized. The target products were obtained via cyclization, chlorination, substitution, cyclization, substituted with phthalic anhydride used as the starting material. The structures of target products are confirmed by 1H NMR, I3C NMR, HRMS. A series of 3,6-substituted-1,2,4-triazolo[3,4-a] phthalazine derivatives was evaluated for anticancer activity on four human cancer cell lines including EC-9706, HeLa and MCF-7 by MTT assay. Among them, compound 5d was more cytotoxic against EC-9706 and HeLa cell lines, with IC50 values ranging from 3.9 to 4.5 μmol·L-1, which are superior or comparable to 5-Fuorouracil. Flow cytometry analysis indicated that compound 5d induced the cellular early apoptosis and cell cycle arrest in G2/M phase in EC-9706.
With the aim of obtaining potential antitumor candidates with more efficiency and more economic value. A series of 3,6-substituted-1,2,4-triazolo[3,4-a]phthalazine derivatives were synthesized. The target products were obtained via cyclization, chlorination, substitution, cyclization, substituted with phthalic anhydride used as the starting material. The structures of target products are confirmed by 1H NMR, I3C NMR, HRMS. A series of 3,6-substituted-1,2,4-triazolo[3,4-a] phthalazine derivatives was evaluated for anticancer activity on four human cancer cell lines including EC-9706, HeLa and MCF-7 by MTT assay. Among them, compound 5d was more cytotoxic against EC-9706 and HeLa cell lines, with IC50 values ranging from 3.9 to 4.5 μmol·L-1, which are superior or comparable to 5-Fuorouracil. Flow cytometry analysis indicated that compound 5d induced the cellular early apoptosis and cell cycle arrest in G2/M phase in EC-9706.
2016, 36(7): 1636-1642
doi: 10.6023/cjoc201602007
Abstract:
The nickel-catalyzed addition and coupling reaction between aryl triflates and aldehydes were developed. The reactions proceed smoothly in the presence of zinc powder with the use of 10 mol% Ni(dppe)Br2 as a catalyst. A range of aryl methanols and aryl ketones were isolated respectively in moderate to good yields in MeOH and THF solvent via direct addition or coupling reactions. Aliphatic and aromatic aldehydes were involved in this reaction, showing a broad substrate scope.
The nickel-catalyzed addition and coupling reaction between aryl triflates and aldehydes were developed. The reactions proceed smoothly in the presence of zinc powder with the use of 10 mol% Ni(dppe)Br2 as a catalyst. A range of aryl methanols and aryl ketones were isolated respectively in moderate to good yields in MeOH and THF solvent via direct addition or coupling reactions. Aliphatic and aromatic aldehydes were involved in this reaction, showing a broad substrate scope.
2016, 36(7): 1643-1652
doi: 10.6023/cjoc201512021
Abstract:
A series of (2-amino-3-(benzothiazol-2-yl)-4H-chromen-4-yl)phosphonate derivatives were synthesized in good to excellent yields by Michael addition/cyclization of diphenyl phosphite to diverse substituted(E)-2-(benzothiazol-2-yl)-3-(2-hydroxyphenyl)acrylonitriles under catalyst-free condition in water. Meanwhile, one-pot three component reaction of salicylaldehyde, 2-(benzothiazol-2-yl)acetonitrile and diphenyl phosphate was also tested using Et3N as catalyst to synthesize these phosphonate derivatives
A series of (2-amino-3-(benzothiazol-2-yl)-4H-chromen-4-yl)phosphonate derivatives were synthesized in good to excellent yields by Michael addition/cyclization of diphenyl phosphite to diverse substituted(E)-2-(benzothiazol-2-yl)-3-(2-hydroxyphenyl)acrylonitriles under catalyst-free condition in water. Meanwhile, one-pot three component reaction of salicylaldehyde, 2-(benzothiazol-2-yl)acetonitrile and diphenyl phosphate was also tested using Et3N as catalyst to synthesize these phosphonate derivatives
2016, 36(7): 1653-1661
doi: 10.6023/cjoc201601011
Abstract:
A series of novel coumarin derivatives containing sulfinic esters or sulfonamide were designed and synthesized. Their structures were characterized by 1H NMR, 13C NMR and elemental analysis. The preliminary bioassays indicated that several target compounds exhibited good in vitro antitumor activities on A549 (up to 67.82%), Bel7402 (up to 58.47%) and HCT-8 (up to 74.80%) at 5.0 mg/L and moderate antifungal activities on Physalospora piricola (up to 82.0 %) at 50 mg/L. The structure-activity relationship of these target compounds was discussed accordingly.
A series of novel coumarin derivatives containing sulfinic esters or sulfonamide were designed and synthesized. Their structures were characterized by 1H NMR, 13C NMR and elemental analysis. The preliminary bioassays indicated that several target compounds exhibited good in vitro antitumor activities on A549 (up to 67.82%), Bel7402 (up to 58.47%) and HCT-8 (up to 74.80%) at 5.0 mg/L and moderate antifungal activities on Physalospora piricola (up to 82.0 %) at 50 mg/L. The structure-activity relationship of these target compounds was discussed accordingly.
2016, 36(7): 1662-1667
doi: 10.6023/cjoc201601026
Abstract:
A one-pot synthetic approach to new fused heterocyclic skeleton 12H, 14H-quinazolino[3, 4-a]-3, 1-benzoxazine by Staudinger/aza-Wittig sequence has been developed. The sequential reaction of azides 3 with triphenylphosphine and acyl chlorides or CS2 produced 12H, 14H-quinazolino[3, 4-a]-3, 1-benzoxazines 5 or 6 in good yields via a consecutive Staudinger/ aza-Wittig/ cyclization reaction.
A one-pot synthetic approach to new fused heterocyclic skeleton 12H, 14H-quinazolino[3, 4-a]-3, 1-benzoxazine by Staudinger/aza-Wittig sequence has been developed. The sequential reaction of azides 3 with triphenylphosphine and acyl chlorides or CS2 produced 12H, 14H-quinazolino[3, 4-a]-3, 1-benzoxazines 5 or 6 in good yields via a consecutive Staudinger/ aza-Wittig/ cyclization reaction.
2016, 36(7): 1668-1671
doi: 10.6023/cjoc201601004
Abstract:
A novel type of hollow aromatic helices was prepared according to an improved organic synthesis approach. By means of UV-Vis spectroscopy, the recognition and selectivity of aromatic helix (AH) for alkali metal ions were investigated. The results indicated that AH could specifically recognize the alkali metal ions with an order of Rb+ > K+ > Cs+ > Na+ > Li+. In addition, the fluorescence titration was carried out by adding Rb+ into the AH solution, which further underpinned the binding capacity and sensitive responsiveness of AH for the alkali metal ions.
A novel type of hollow aromatic helices was prepared according to an improved organic synthesis approach. By means of UV-Vis spectroscopy, the recognition and selectivity of aromatic helix (AH) for alkali metal ions were investigated. The results indicated that AH could specifically recognize the alkali metal ions with an order of Rb+ > K+ > Cs+ > Na+ > Li+. In addition, the fluorescence titration was carried out by adding Rb+ into the AH solution, which further underpinned the binding capacity and sensitive responsiveness of AH for the alkali metal ions.
2016, 36(7): 1672-1676
doi: 10.6023/cjoc201512007
Abstract:
An easy and efficient "one-pot" synthetic method facilitated by Fe to synthesize substituted 1-phenyl-1H-benzimi-dazole has been developed successfully. By using liquid organic acid as solvent, 2-nitro-N-phenylaniline is converted to substituted 1-phenyl-1H-benzimidazole directly after reduction and cyclization catalyzed by Fe, with the yield of 80%~92%. Through the application of high performance liquid chromatography (HPLC) detection, the effects of the amount of solvent, the type of liquid organic acid, temperature and reaction time on the "one-pot" reaction have been fully investigated, as well as the reaction mechanism. The "one-pot" method proposed here has multiple advantages, such as mild condition, easy procedure, cheap ingredients and high yield, which provide a newly convenient synthetic route.
An easy and efficient "one-pot" synthetic method facilitated by Fe to synthesize substituted 1-phenyl-1H-benzimi-dazole has been developed successfully. By using liquid organic acid as solvent, 2-nitro-N-phenylaniline is converted to substituted 1-phenyl-1H-benzimidazole directly after reduction and cyclization catalyzed by Fe, with the yield of 80%~92%. Through the application of high performance liquid chromatography (HPLC) detection, the effects of the amount of solvent, the type of liquid organic acid, temperature and reaction time on the "one-pot" reaction have been fully investigated, as well as the reaction mechanism. The "one-pot" method proposed here has multiple advantages, such as mild condition, easy procedure, cheap ingredients and high yield, which provide a newly convenient synthetic route.
2016, 36(7): 1677-1680
doi: 10.6023/cjoc201602002
Abstract:
Two diterpenoids and a few miscellaneous components (one phenethylpropanoid, one flavonoid, and one lignan) were isolated from the MeOH extract of the whole plant of the rare Chloranthaceae plant Chloranthus sessilifolius during a further phytochemical reinvestigation. Based on their spectroscopic data (i.e., IR, UV, 1D/2D NMR, ECD, and HR-ESIMS) and/or comparing with those reported physicochemical data in related literature, the structures were determined to be (3R, 5S, 6S, 9S, 10S, 13S)-3, 6, 13-trihydroxy-ent-abieta-8(14)-en-7-one (1), 3α, 15-dihydroxy-13α-methoxy-ent-abieta-8(14)-en-7-one (2), p-coumaroyl-β-phenethyl amine (3), narigenin trimethyl ether (4), and (3R, 4R, 3'R, 4'R)-6, 6'-dimethoxy-3, 4, 3', 4'-tetrahydro-2H, 2H'-[3, 3']-bichromenyl-4, 4'-diol (5). Among them, compound 1 is new, while compounds 3~5 were isolated from the Chloranthus genus for the first time.
Two diterpenoids and a few miscellaneous components (one phenethylpropanoid, one flavonoid, and one lignan) were isolated from the MeOH extract of the whole plant of the rare Chloranthaceae plant Chloranthus sessilifolius during a further phytochemical reinvestigation. Based on their spectroscopic data (i.e., IR, UV, 1D/2D NMR, ECD, and HR-ESIMS) and/or comparing with those reported physicochemical data in related literature, the structures were determined to be (3R, 5S, 6S, 9S, 10S, 13S)-3, 6, 13-trihydroxy-ent-abieta-8(14)-en-7-one (1), 3α, 15-dihydroxy-13α-methoxy-ent-abieta-8(14)-en-7-one (2), p-coumaroyl-β-phenethyl amine (3), narigenin trimethyl ether (4), and (3R, 4R, 3'R, 4'R)-6, 6'-dimethoxy-3, 4, 3', 4'-tetrahydro-2H, 2H'-[3, 3']-bichromenyl-4, 4'-diol (5). Among them, compound 1 is new, while compounds 3~5 were isolated from the Chloranthus genus for the first time.
2016, 36(7): 1681-1685
doi: 10.6023/cjoc201601034
Abstract:
A tetra-butyl ammonium iodide (TBAI)-catalyzed oxidative dehydrogenation of β-acylamino ketones for the synthesis of Z-β-acylamino enones has been developed. The present method has some distinct advantages such as mild conditions, high selectivity, readily available starting materials, and broad substrate scope. This method is also the first example of oxidative dehydrogenation with the use of TBAI/TBHP (tert-butyl hydroperoxide) oxidation system.
A tetra-butyl ammonium iodide (TBAI)-catalyzed oxidative dehydrogenation of β-acylamino ketones for the synthesis of Z-β-acylamino enones has been developed. The present method has some distinct advantages such as mild conditions, high selectivity, readily available starting materials, and broad substrate scope. This method is also the first example of oxidative dehydrogenation with the use of TBAI/TBHP (tert-butyl hydroperoxide) oxidation system.
2016, 36(7): 1686-1689
doi: 10.6023/cjoc201601035
Abstract:
Two new rearranged lanostane triterpenoids, named tsugalide A (1) and tsugalide B (2), were isolated from the MeOH extract of the stem of Tsuga longibracteata Cheng. Their chemical structures of the new compounds were established on the basis of extensive 1D and 2D NMR spectroscopy, and the configuration of compound 1 was further confirmed by X-ray crystallography.
Two new rearranged lanostane triterpenoids, named tsugalide A (1) and tsugalide B (2), were isolated from the MeOH extract of the stem of Tsuga longibracteata Cheng. Their chemical structures of the new compounds were established on the basis of extensive 1D and 2D NMR spectroscopy, and the configuration of compound 1 was further confirmed by X-ray crystallography.
2016, 36(7): 1690-1695
doi: 10.6023/cjoc201602003
Abstract:
For exploring a simple and efficient synthetic method of C-glycosides, (2, 3-O-isopropylidene)-β-C-D-ribosyl ethyl acetate and (2, 3-O-isopropylidene)-β-C-D-ribosyl acetic acid were stereospecifically synthesized by a one-pot tandem Wittig-Michael addition reaction, and then treated with corresponding base, respectively. The acetates were reduced by DIBAL-H to obtain the corresponding glycosyl aldehyde. D-xylose was treated following the procedure of acetonide of 1, 2-position, trifluoroacetoxyation of 3, 5-position. The trifluoroacetoxyl groups were substituted by azido groups, followed by the one-pot tandem Wittig-Michael addition reaction, and then treated with corresponding base. 3, 5-Diazido-β-C-D-ribosyl acetic acid was obtained in high stereo specificity.
For exploring a simple and efficient synthetic method of C-glycosides, (2, 3-O-isopropylidene)-β-C-D-ribosyl ethyl acetate and (2, 3-O-isopropylidene)-β-C-D-ribosyl acetic acid were stereospecifically synthesized by a one-pot tandem Wittig-Michael addition reaction, and then treated with corresponding base, respectively. The acetates were reduced by DIBAL-H to obtain the corresponding glycosyl aldehyde. D-xylose was treated following the procedure of acetonide of 1, 2-position, trifluoroacetoxyation of 3, 5-position. The trifluoroacetoxyl groups were substituted by azido groups, followed by the one-pot tandem Wittig-Michael addition reaction, and then treated with corresponding base. 3, 5-Diazido-β-C-D-ribosyl acetic acid was obtained in high stereo specificity.
2016, 36(7): 1696-1699
doi: 10.6023/cjoc201602016
Abstract:
The genomic sequences of Streptomyces sp. TP-A0365 were scanned using a secondary metabolite genome mining approach. A new nonribosomal peptide synthetase (NRPS) gene responsible for the biosynthesis of an unknown pyrazinone compound was found. The biosynthetic pathway of related compound was disrupted by inactivating the NRPS gene. Comparing the fermentation products of the mutant strain and the original strain (TG1301 derived from Streptomyces sp. TP-A0365), we caught compound 1 which disappeared in the mutant strain. Compound 1 was isolated from 20 L fermentation cultures of the original strain and its structure was established as 3-isopropyl-7, 8-dihydropyrrolo[1, 2-a]pyrazin-4(6H)-one, a new pyrazinone compound designated as provalin
The genomic sequences of Streptomyces sp. TP-A0365 were scanned using a secondary metabolite genome mining approach. A new nonribosomal peptide synthetase (NRPS) gene responsible for the biosynthesis of an unknown pyrazinone compound was found. The biosynthetic pathway of related compound was disrupted by inactivating the NRPS gene. Comparing the fermentation products of the mutant strain and the original strain (TG1301 derived from Streptomyces sp. TP-A0365), we caught compound 1 which disappeared in the mutant strain. Compound 1 was isolated from 20 L fermentation cultures of the original strain and its structure was established as 3-isopropyl-7, 8-dihydropyrrolo[1, 2-a]pyrazin-4(6H)-one, a new pyrazinone compound designated as provalin
2016, 36(7): 1700-1705
doi: 10.6023/cjoc201511020
Abstract:
A novel water-soluble asymmetric trimethine cyanine dye which contains one nonionic hydrophilic group was first synthesized, which was prepared from one-step synthesis with N-carboxybenzyl-2, 3, 3-trimethyl-3H-indol-5-sulfonic acid, N, N′-diphenylformamidine and 2, 3, 3-trimethyl-3H-indol-5-sulfonic acid with PEG. The pure title compound could be obtained by using the self-made C18 reversed-phase chromatographic column. The structure of the product was identified by NMR and HRMS. The spectra character and photostability of this dye were detected, protein labeling of albumin bovine serum (BSA) and cell stain with this dye were investigated. The results showed that the yield of the target compound could reach 73% by simple synthesis and purification, the fluorescence quantum yield was 0.3, the D/P of protein labeling was 1.87. The dye could effectively distinguish between the fixed cells and living cells, because of the significant differences in the staining results.
A novel water-soluble asymmetric trimethine cyanine dye which contains one nonionic hydrophilic group was first synthesized, which was prepared from one-step synthesis with N-carboxybenzyl-2, 3, 3-trimethyl-3H-indol-5-sulfonic acid, N, N′-diphenylformamidine and 2, 3, 3-trimethyl-3H-indol-5-sulfonic acid with PEG. The pure title compound could be obtained by using the self-made C18 reversed-phase chromatographic column. The structure of the product was identified by NMR and HRMS. The spectra character and photostability of this dye were detected, protein labeling of albumin bovine serum (BSA) and cell stain with this dye were investigated. The results showed that the yield of the target compound could reach 73% by simple synthesis and purification, the fluorescence quantum yield was 0.3, the D/P of protein labeling was 1.87. The dye could effectively distinguish between the fixed cells and living cells, because of the significant differences in the staining results.
2016, 36(7): 1706-1711
doi: 10.6023/cjoc201512025
Abstract:
A facile and rapid synthesis of 8-aryl-5, 7, 7-tricyanoisoquinoline derivatives from the reaction of aromatic aldehydes, malononitrile, and N-substituted-4-piperidones at room temperature under solvent-free and catalyst-free conditions. The N-ethylpiperidin-4-one was first used for the synthesis of 6-amino-2-ethyl-8-aryl-2, 3, 8, 8a-tetrahydroisoquinoline-5, 7, 7(1H)-tricarbonitrile derivatives. This method offers several advantages in terms of its mild conditions, available raw materials, simple operation, high yields, short reaction time and green process. The products were identified by IR, 1H NMR and HRMS. The reported method is the efficient approach for the synthesis of isoquinoline derivatives.
A facile and rapid synthesis of 8-aryl-5, 7, 7-tricyanoisoquinoline derivatives from the reaction of aromatic aldehydes, malononitrile, and N-substituted-4-piperidones at room temperature under solvent-free and catalyst-free conditions. The N-ethylpiperidin-4-one was first used for the synthesis of 6-amino-2-ethyl-8-aryl-2, 3, 8, 8a-tetrahydroisoquinoline-5, 7, 7(1H)-tricarbonitrile derivatives. This method offers several advantages in terms of its mild conditions, available raw materials, simple operation, high yields, short reaction time and green process. The products were identified by IR, 1H NMR and HRMS. The reported method is the efficient approach for the synthesis of isoquinoline derivatives.
