The First Total Synthesis of Natural 6β-Cinnamoyloxy-1α- hydroxy-5, 10-bis-epi-eudesm-4-en-3-one

The first total synthesis of natural 6β-cinnamoyloxy-1α-hydroxy-5, 10-bis-epi- eudesm-4-en-3-one （1）, a highly complex natural eudesmane, was described.

Stereoselective Synthesis of 3(R) and 3(S)-Hydroxyeicos-4(E)-en-1-yne, a Component of the Marine Sponge Cribrochalina Vasculum

Stereocontrolled synthesis of 3(R) and 3(S)-hydroxyeicos-4(E)-en-1-yne has been achieved through double elimination of chloride intermediates 8 and 11, which were prepared from acetylenic alcohol intermediates 1 and 10.

A Triterpenoid Inhibited Hormone-Induced Adipocyte Differentiation and Alleviated Dexamethasone-Induced Insulin Resistance in 3T3-L1 adipocytes

6a-Hydroxylup-20(29)-en-3-on-28-oic acid(1),a natural triterpenoid,was found to possess the ability in a dose-dependent manner inhibiting hormone-induced adipocyte differentiation in 3T3-L1 preadipocytes,and restoring glucose consuming ability in dexamethasone(DXM)-induced insulin resistant 3T3-L1 adipocytes.Compound 1 was also found to ameliorate DXM-induced adipocyte dysfunction in lipolysis and adipokine secretion.Mechanistic studies revealed that 1 inhibited adipocyte differentiation in 3T3-L1 preadipocytes via down-regulating hormone-stimulated gene transcription of peroxisome proliferator-activated receptor c and CCAAT-enhancer-binding protein alpha which are key factors in lipogenesis,and restored DXM-impaired glucose consuming ability in differentiated 3T3-L1 adipocytes via repairing insulin signaling pathway and activating down-stream signaling transduction by phosphorylation of signaling molecules PI3K/p85,Akt2 and AS160,thus leading to increased translocation of glucose transporter type 4 and transportation of glucose.

Synthesis of Gingerenone C and 5-Hydroxy-1-(4′-hydroxy-3-methoxyphenyl)-7-(4′′-hydroxyphenyl)-3-heptanone

The two diarylheptanoids (E)-1-(4-hydroxy-3-methoxyphenyl)-7-(4-hydroxyphenyl) hept-4-en-3-one 1 (Gingerenone C) and (±)-5-hydroxy-1-(4-hydroxy-3-methoxyphenyl)-7-(4- hydroxyphenyl)-3-heptanone 2 were synthesized from vanillin 3 and 4-hydroxybenzaldehyde 9.

Antiviral stereoisomers of 3,5-bis(2-hydroxybut-3-en-1-yl)-1,2,4-thiadiazole from the roots of Isatis indigotica

Four stereoisomers of 3,5-bis（2-hydroxybut-3-en-1-yl）-l,2,4-thiadiazole, named insatindigothiadia- zoles A-D （1a-1d）, were isolated from the roots oflsatis indigotica. Their structures were determined by spectroscopic analysis; specifically, the absolute configurations were assigned by using the MPA determination rule based on △δrs values of MPA esters, and supported by electronic CD （ECD） calculations. Proposed biosynthetic pathways and preliminary investigations of the biological activities of la-1d against influenza virus A （H3N2）, Coxsackie virus B3, and/or HSV-1 are also discussed.

Synthesis and Fungicidal Activity of （E）-5-[1-（2-Oxo- 1 -oxaspiro[4,5]dec/non-3-en-3-yl）ethylidene]-2- aminoimidazolin-4-one Derivatives

The novel fungicidal agents, （E）-5-[1-（2-oxo-l-oxaspiro[4,5]dec/non-3-en-3-yl）ethylidene]-2-aminoimidazolin- 4-one derivatives, were designed and synthesized in moderate to excellent yields in four steps using a-hydroxyketone and diketene as raw materials and characterized by HR-ESI-MS, 1H NMR and X-ray diffraction. The preliminary bioassay showed that some of these compounds, such as 5e, 6a, 6e, and 7h exhibit 87.8%, 91.3%, 89.9% and 87.8% inhibition rates against Sclerotinia scleotiorum, 3b, 3c, 4c and 7h exhibit 96.4%, 92.5%, 90.3% and 76.9% inhibition rates against Phytophthora capsici at the concentration of 50 μg/mL, respectively. These compounds exhibited significant fungicidal activities against S. scleotiorum and P. capsici with EC50 values of 2.56 --11.60 μg/mL, and compounds 6e and 7h exhibited weak inhibition against the spore germination of S. scleoti- orum, while the spore germination ofP. capsici was strongly inhibited by compound 7h solution. Scanning electron microscopy （SEM） and transmission electron microscopy （TEM） observation indicated that compound 7h had a significant impact on the structure and function of the hyphal cell wall ofP. capsici mycelium.

Visible-Light-Promoted Formation of C-C and C-P Bonds Derived from Evolution of Bromoalkynes under Additive-Free Conditions:Synthesis of 1,1-Dibromo-1-en-3-ynes and Alkynylphosphine Oxides

Main observation and conclusion The controllable achievement of C-C and C-P bond formations is developed via visible-light-promoted bromoalkyne dimerization or its further transformation with secondary phosphine oxides.The 1,1-dibromo-1-en-3-ynes are formed when bromoalkyne is exposed to visible-light.While alkynylphosphine oxides are generated when bromoalkynes are mixed with secondary phosphine oxides.

红蓼果实中的一个新三萜皂苷(英文)

为了研究红蓼果实的化学成分,利用硅胶和反相柱色谱方法进行分离纯化,根据理化性质和光谱数据鉴定其化合物结构,分离并鉴定了3个化合物:28-O-β-D-glucopyranosyl-3β,7β-dihydroxy-lup-20(29)-en-28-oate(1),5,7-二羟基色原酮(2)和柚皮素(3)。化合物1为新化合物,化合物2,3为首次从该植物中分离得到。

吉祥草的化学成分研究

目的：对吉祥草的化学成分进行研究。方法：利用萃取，硅胶、凝胶和反相硅胶柱色谱以及高效液相色谱法进行分离和纯化，采用谱学技术（1D和2D NMR谱，MS，IR等）进行结构鉴定。结果：从吉祥草中分离鉴定了6个化合物，分别是1α，3β-dihydroxy-5β-pregn-16-en-20-one 3-O-β-D-glucopyranoside（1），syringaresinol-β-D-gluco-side（2），sophoraflavoneB（3），stigmast-5，22-dien-3-O-β-D-glucopyranoside（4），胡萝卜苷（5），α-D-glucose（6）。结论：化合物1为新化合物，化合物2～6为首次从该植物中分离得到。

Two New Pentacyclic Triterpenes from Sabia parviflora

Two new pentacyclic triterpene acids, 1a, 3b-dihydroxyl-olean-12-en-28-oic acid and 1a, 2a, 3b-trihydroxyl-olean-12-en-28-oic acid, were isolated from the arial parts of Sabia parviflora.

Recent advances on controllable and selective catalytic oxidation of cyclohexene

Because of multiple potential reaction sites and variable oxidation depths,oxidation of cyclohexene can lead to a mixture of products with different oxidation states and functional groups,such as 7-oxabicyclo[4.1.0]heptane,trans/cis-cyclohexane-1,2-diol,cyclohex-2-en-1-ol,cyclohex-2-en-1-one,and even adipic acid.These products are broadly and abundantly used intermediates in the chemical industry;therefore,controllable oxidation reactions for cyclohexene that can selectively afford the targeted products are synthetically valuable for applications in both the academy and industry,thus becoming the aim of synthetic and catalytic chemists in the field.Many reports on selective oxidation of cyclohexene have recently appeared in the literature because of its significance.This short review summarizes the recent advances on this subject,and the contents are mainly classified based on the chosen oxidants.We hope that this review can provide a useful guide for controllable and selective catalytic oxidation of cyclohexene for interested readers from both the academy and industry.

A new triterpene and a saponin from Centella asiatica

A new triterpene and a saponin, named 2α,3β23-trihydroxyurs-20-en-28-oic acid （1） and 2α,3β,23-trihydroxyurs-20-en-28-oic acid O-α-L-rhanmopyranosyl-（1→4）-O-β-D-glucopyranosyl-（1→6）-O-β-D-glucopyranosyl ester （2）, have been isolated from the aerial part of CenteUa asiatica. Their structures were elucidated by spectral methods, including 2D-NMR spectra.

Two Eremophilane-type Sesquiterpenoids from the Rhizomes of Ligularia veitchiana(Hemsl.) Greenm

Two eremophilane-type sesquiterpenoids from the rhizomes of Ligularia veitchiana（Hemsl.） Greenm were isolated and determined as 10α,11-endoperoxide-1（2）-en-7α-hydroeremophilane（1） and 1（10）-en-2-oxo-7α-isopropanol-eremophilane（2）.Compound 1 was a new compound and compound 2 was a new natural product.The structures of the two compounds were established by means of spectral methods including 1^H NMR,13^C NMR,2D NMR and MS.

Two new aristolane sesquiterpenes from Laurencia similis

Two new aristolane sesquiterpenes, namely, aristolan-10-ol-9-one and aristolan-8-en-1-one, were isolated from the red alga Laurencia similis. Their structures were established on the basis of various NMR spectroscopic analyses, including 2D NMR techniques ((1)H–(1)H COSY, HMQC, HMBC, and NOESY) and HR-FAB-MS.

Photooxidation of α-Tocopherol in Micelles. A New Singlet Oxygen Oxidation Product

Methylene blue sensitized singlet oxygen oxidation of dl-α-tocopherol in dodecylsulfate (SDS) or cetyl trimethyl ammonium brondde (CTAB) ndcelles led to the formation, besidesα-tocopherol quinone and its epoxide, of a hitherto unknown spiro compound 6-hydroxy-2,6,8,9-tetramethyl-2-phytyl- 1-oxaspiro [4, 5] dec -8 - en - 7, 10-dione.

Bioactive Compounds and Insecticidal Activity of Hysterionica pinifolia, a Native South American Plant

Phytochemical investigation of the purified fractions of the active dichloromethane extract of Hysterionica pinifolia (Poir.) Baker led to the identification of five compounds. New acetylenic alcohol (E)-undec-3-en-5,7-diyne-1-ol (1) and three other compounds (3), (4), and (5) were reported for the first time in this species. Furthermore, forty-six components from the volatile fraction of H. pinifolia were identified. These compounds were elucidated using 1D and 2D NMR spectroscopy as well as MS-ESI and GC-FID-MS experiments. The dichloromethane extract, its fractions, and the methanolic extract were tested for insecticidal activity against Tribolium castaneum under laboratory conditions. The dichloromethane extract and the fraction F2 were found to be active, showing high larval mortality. The dichloromethane extract was also active against T. castaneum adults. The results have shown that H. pinifolia could be considered, in a near future, as a potential source for the development of a botanical insecticide for pest control.

Co-Catalyzed Dehydrogenation Claisen Condensation of Secondary Alcohols with Esters

Comprehensive Summary Catalytic dehydrogenation,with its exceptional atom economy and chemoselectivity,offers a highly desirable yet challenging approach for converting multiple environmentally friendly alcohols into crucial molecules.Furthermore,the utilization of catalysts based on abundant elements found on Earth for alcohol dehydrogenation to produce acryl ketone holds significant promise as a versatile strategy in synthesizing key building blocks for numerous pharmaceutical applications.The present study describes a practical Co-catalyzed cascade dehydrogenative Claisen condensation of secondary alcohols with esters,facilitating the synthesis of a wide range of 3-hydroxy-prop-2-en-1-ones.We introduce a catalytic system based on novel and scalable indazole NNP-ligands coordinated to cobalt for efficient dehydrogenations of secondary alcohols,and propose a plausible reaction mechanism supported by control experiments and labeling studies.Notably,it allows for the streamlined synthesis of multiple pharmaceuticals in one-pot.

山沉香中两个新倍半萜的结构鉴定和抗菌活性(英文)

目的:对山沉香中化学成分的分离鉴定和抗菌活性进行研究。方法:运用柱层析等方法对山沉香氯仿层进行分离纯化,并通过波谱解析和理化鉴别进行结构鉴定。同时对分离得到化合物的抗菌活性进行了评估。结果:从山沉香分离得到2个倍半萜类化合物:guai-9-en-4β-ol(1)和14, 15-dinorguai-1, 11-dien-9, 10-dione(2)。化合物1对Bacillus coagulas具有良好的活性而对Proteous vulgaris活性较差; 化合物2对Eschecheria coli具有良好的活性而对Staphylococcus aureus活性较差。结论:化合物1和2为新化合物, 具有较好的抗菌活性。

川赤芍的化学成分分离鉴定

目的:研究川赤芍的化学成分。方法:取川赤芍(30 kg),用95%乙醇回流提取4次,提取液过滤后合并,减压浓缩得浸膏,将浸膏加水混悬后依次用石油醚、二氯甲烷、乙酸乙酯、正丁醇进行萃取,得到相应的5个部位,石油醚部分、二氯甲烷部分、乙酸乙酯部分、正丁醇部分和水部分。各部位分别采用硅胶,Sephadex LH-20,ODS柱色谱及中压制备液相,高压制备液相等方法对其进行分离纯化,得到的化合物用红外、质谱、核磁共振谱等波谱技术进行鉴定。结果:从川赤芍中分离纯化得到16个化合物,分别鉴定为(1S,5R,6R)-1,8-dihydroxypin-2-en-4-one (1),(2-hydroxyl)-phenyl-methyl-β-D-xylopyranoside(2),flufuran (3),6’-O-vanillylpaeoniflorin (4),2,5-二羟基肉桂酸甲酯(5),(1S,2S,5R,6R)-1,8-dihydroxypin-4-one (6),palbinone (7),4-O-甲基芍药苷(8),4-O-乙基芍药苷(9),苯甲酰氧化芍药苷(10),苯甲酸(11),没食子酸(12),没食子酸甲酯(13),没食子酸乙酯(14),β-谷甾醇(15),1,2,3,4,6-O-五没食子酰葡萄糖(16)。结论:其中,化合物1,2为新的天然化合物,化合物3为首次从芍药属中分离得到,化合物4~7为首次从该植物中分离得到。