以过氧磷钼钨酸十六烷基吡啶盐Cat-PMo2W2O24为催化剂,质量分数为30%的H2O2为氧化剂,催化3-蒈烯选择性环氧化合成3,4-环氧蒈烷。考察了溶剂种类、反应温度、催化剂用量、H2O2用量及反应时间对底物转化率与环氧选择性的影响,确定了最佳...以过氧磷钼钨酸十六烷基吡啶盐Cat-PMo2W2O24为催化剂,质量分数为30%的H2O2为氧化剂,催化3-蒈烯选择性环氧化合成3,4-环氧蒈烷。考察了溶剂种类、反应温度、催化剂用量、H2O2用量及反应时间对底物转化率与环氧选择性的影响,确定了最佳反应条件为:3-蒈烯12 mmol,溶剂三氯甲烷5 m L,催化剂用量为2.45%(即其质量与3-蒈烯质量的百分数,下同),H2O2与3-蒈烯摩尔比值为1.1,反应温度35℃,反应时间6 h;在最佳条件下,3-蒈烯的转化率和3,4-环氧蒈烷的选择性分别为99.1%和94.8%。展开更多
The first total synthesis of （+）-5α-hydroxy-isopterocarpolone （1）, an oxygenated eudesmane isolated from Chinese folk medicine Artemisia eriopoda, starting from （+）-dihydrocarvone（2） was described. Compound 4...The first total synthesis of （+）-5α-hydroxy-isopterocarpolone （1）, an oxygenated eudesmane isolated from Chinese folk medicine Artemisia eriopoda, starting from （+）-dihydrocarvone（2） was described. Compound 4 was stereoselectively prepared from compound 2 in three steps according to reference-. The treatment of tosylhydrazone 5, which was formed via the reaction of compound 4 and TsNHNH2 catalyzed by BF3-5Et2O, with an excess of n-butyllithium gave triene 6. Oxidation of triene 6 with singlet oxygen afforded the desired endo-peroxide 7 as a single product. Reductive cleavage of peroxide 7 with K2CO3 gave α-rotunol 3, a natural eudesmane firstly isolated in 1969. Hydrolysis of α-rotunol 3 with 10% sulfuric acid afforded （+）-5α-hydroxy-isopterocarpolone （1）. The structures of all the compounds were confirmed by IR, MS and NMR spectra.展开更多
3-Oxo-11,12,13-trihydroxyeudesm-4-ene(1) was a highly oxygenated natural eudesmane isolated from traditional herbal medicine with an antiphlogostic and spasmolytic activity.For the purpose of pharmacological activity ...3-Oxo-11,12,13-trihydroxyeudesm-4-ene(1) was a highly oxygenated natural eudesmane isolated from traditional herbal medicine with an antiphlogostic and spasmolytic activity.For the purpose of pharmacological activity research on natural product 1 and its derivatives,a facile total synthesis of compound 1 starting from(+)-dihydrocarvone(2) was completed in an overall yield of 24%.The structures of all intermediates and product 1 were confirmed via 1H NMR,13C NMR,MS and IR techniques.The NMR data of compound 1 are in agreement with those of natural products.展开更多
(Z)-3-dodecen-1-yl(E)-2-butenoate was synthesized starting from acetylene. The key feature of this approach is use of ethylene diamine in the reaction of acetylene and sodium amide for synthesizing 1-decyne. This reac...(Z)-3-dodecen-1-yl(E)-2-butenoate was synthesized starting from acetylene. The key feature of this approach is use of ethylene diamine in the reaction of acetylene and sodium amide for synthesizing 1-decyne. This reaction allowed a convenient preparation of terminal alkyne with a long chain from cheap and common chemicals. The title sex pheromone synthesized showed highly attractant activity in the field to cylas formicarius fabricius.展开更多
A facile and efficient diastereoselective synthesis of methyl 3β-hydroxyeudesmane-4,11(13)-dien-12-oicate starting from (+)-dihydrocarvone has been carried out in 9 steps at the first time.
14-Noreudesma-4,11-dien-3,9-diones′ analogues were treated with DDQ in dioxane and afforded the rearranged aromatic products. The similar compounds to eudesma-4,11-dien-3,9-diones had no reaction. 9-Actoxy-14-noreude...14-Noreudesma-4,11-dien-3,9-diones′ analogues were treated with DDQ in dioxane and afforded the rearranged aromatic products. The similar compounds to eudesma-4,11-dien-3,9-diones had no reaction. 9-Actoxy-14-noreudesma-4,11-dien-3-ones, 9-actoxy-eudesma-4,11-dien-3-ones and their analogues yielded the normal 1,2-dehydro-products. The mechanism of the rearrangement was discussed.展开更多
A compound ethyl(5S,6R)-2-(4-methylphenyl)-6-[(1R)-tert-butyldimethylsilyloxyethy]-penem-3-carboxylate was synthesized through displacement,acylation and Wittig cyclization reaction of optically active material(3R,4R)...A compound ethyl(5S,6R)-2-(4-methylphenyl)-6-[(1R)-tert-butyldimethylsilyloxyethy]-penem-3-carboxylate was synthesized through displacement,acylation and Wittig cyclization reaction of optically active material(3R,4R)-3-[(1R)-tert-butyldimethylsilyloxyethyl]-4-acetoxy-2-azetidi-none(4AA)upon thionocarboxlic acid.The intermediates and the target product were characterized by 1HNMR,IR,elementary analysis and MS.展开更多
将α-蒎烯选择性氧化制备马鞭草烯酮,对羰基进行肟化和分离,再发生亲核取代反应,合成得到40个新型( Z )-/( E )-马鞭草烯酮肟醚(4a ~4t ,包括20对 Z / E 异构体),采用 1 H NMR、 13 C NMR 、FT-IR、UV-vis和ESI-MS对目标化合物进行了结...将α-蒎烯选择性氧化制备马鞭草烯酮,对羰基进行肟化和分离,再发生亲核取代反应,合成得到40个新型( Z )-/( E )-马鞭草烯酮肟醚(4a ~4t ,包括20对 Z / E 异构体),采用 1 H NMR、 13 C NMR 、FT-IR、UV-vis和ESI-MS对目标化合物进行了结构表征,并测试其抑菌活性。研究结果表明:在质量浓度50 mg/L下,目标化合物对8种植物病原菌均显示出不同程度的抑菌活性,其中化合物( E )- 4r (R=2,6-Cl)对苹果轮纹病菌的抑制率为77.8%,化合物( E )- 4s (R=2,6-F)对水稻纹枯病菌的抑制率为72.7%,化合物( E )- 4n (R= p -CN)对玉米小斑病菌的抑制率为70.8%,( Z )-/( E )-异构体对一些植物病原菌的抑制活性显示一定差异。建立了( E )-马鞭草烯酮肟醚化合物对水稻纹枯病菌抑制活性的CoMFA模型( r 2 =0.992, q 2 =0.507),进行3D-QSAR研究,结果表明建立的模型可用于设计具有潜在高活性的先导化合物。展开更多
文摘以过氧磷钼钨酸十六烷基吡啶盐Cat-PMo2W2O24为催化剂,质量分数为30%的H2O2为氧化剂,催化3-蒈烯选择性环氧化合成3,4-环氧蒈烷。考察了溶剂种类、反应温度、催化剂用量、H2O2用量及反应时间对底物转化率与环氧选择性的影响,确定了最佳反应条件为:3-蒈烯12 mmol,溶剂三氯甲烷5 m L,催化剂用量为2.45%(即其质量与3-蒈烯质量的百分数,下同),H2O2与3-蒈烯摩尔比值为1.1,反应温度35℃,反应时间6 h;在最佳条件下,3-蒈烯的转化率和3,4-环氧蒈烷的选择性分别为99.1%和94.8%。
文摘The first total synthesis of （+）-5α-hydroxy-isopterocarpolone （1）, an oxygenated eudesmane isolated from Chinese folk medicine Artemisia eriopoda, starting from （+）-dihydrocarvone（2） was described. Compound 4 was stereoselectively prepared from compound 2 in three steps according to reference-. The treatment of tosylhydrazone 5, which was formed via the reaction of compound 4 and TsNHNH2 catalyzed by BF3-5Et2O, with an excess of n-butyllithium gave triene 6. Oxidation of triene 6 with singlet oxygen afforded the desired endo-peroxide 7 as a single product. Reductive cleavage of peroxide 7 with K2CO3 gave α-rotunol 3, a natural eudesmane firstly isolated in 1969. Hydrolysis of α-rotunol 3 with 10% sulfuric acid afforded （+）-5α-hydroxy-isopterocarpolone （1）. The structures of all the compounds were confirmed by IR, MS and NMR spectra.
文摘3-Oxo-11,12,13-trihydroxyeudesm-4-ene(1) was a highly oxygenated natural eudesmane isolated from traditional herbal medicine with an antiphlogostic and spasmolytic activity.For the purpose of pharmacological activity research on natural product 1 and its derivatives,a facile total synthesis of compound 1 starting from(+)-dihydrocarvone(2) was completed in an overall yield of 24%.The structures of all intermediates and product 1 were confirmed via 1H NMR,13C NMR,MS and IR techniques.The NMR data of compound 1 are in agreement with those of natural products.
文摘(Z)-3-dodecen-1-yl(E)-2-butenoate was synthesized starting from acetylene. The key feature of this approach is use of ethylene diamine in the reaction of acetylene and sodium amide for synthesizing 1-decyne. This reaction allowed a convenient preparation of terminal alkyne with a long chain from cheap and common chemicals. The title sex pheromone synthesized showed highly attractant activity in the field to cylas formicarius fabricius.
文摘A facile and efficient diastereoselective synthesis of methyl 3β-hydroxyeudesmane-4,11(13)-dien-12-oicate starting from (+)-dihydrocarvone has been carried out in 9 steps at the first time.
文摘14-Noreudesma-4,11-dien-3,9-diones′ analogues were treated with DDQ in dioxane and afforded the rearranged aromatic products. The similar compounds to eudesma-4,11-dien-3,9-diones had no reaction. 9-Actoxy-14-noreudesma-4,11-dien-3-ones, 9-actoxy-eudesma-4,11-dien-3-ones and their analogues yielded the normal 1,2-dehydro-products. The mechanism of the rearrangement was discussed.
文摘A compound ethyl(5S,6R)-2-(4-methylphenyl)-6-[(1R)-tert-butyldimethylsilyloxyethy]-penem-3-carboxylate was synthesized through displacement,acylation and Wittig cyclization reaction of optically active material(3R,4R)-3-[(1R)-tert-butyldimethylsilyloxyethyl]-4-acetoxy-2-azetidi-none(4AA)upon thionocarboxlic acid.The intermediates and the target product were characterized by 1HNMR,IR,elementary analysis and MS.
文摘将α-蒎烯选择性氧化制备马鞭草烯酮,对羰基进行肟化和分离,再发生亲核取代反应,合成得到40个新型( Z )-/( E )-马鞭草烯酮肟醚(4a ~4t ,包括20对 Z / E 异构体),采用 1 H NMR、 13 C NMR 、FT-IR、UV-vis和ESI-MS对目标化合物进行了结构表征,并测试其抑菌活性。研究结果表明:在质量浓度50 mg/L下,目标化合物对8种植物病原菌均显示出不同程度的抑菌活性,其中化合物( E )- 4r (R=2,6-Cl)对苹果轮纹病菌的抑制率为77.8%,化合物( E )- 4s (R=2,6-F)对水稻纹枯病菌的抑制率为72.7%,化合物( E )- 4n (R= p -CN)对玉米小斑病菌的抑制率为70.8%,( Z )-/( E )-异构体对一些植物病原菌的抑制活性显示一定差异。建立了( E )-马鞭草烯酮肟醚化合物对水稻纹枯病菌抑制活性的CoMFA模型( r 2 =0.992, q 2 =0.507),进行3D-QSAR研究,结果表明建立的模型可用于设计具有潜在高活性的先导化合物。
