Synthesis of New Fluorinated Podophyllotoxin Derivatives

Five fluorinated podophyUotoxin derivatives were synthesized using dimethylamino-sulfurtrifluoride (DAST).     

羟基查尔酮类衍生物的合成

4-羟基苯乙酮或2,4-二羟基苯乙酮与取代苯甲醛在乙二醇溶液中,以硼酸为催化剂,于110～120℃反应6 h,再经柱分离精制得羟基查尔酮衍生物.产物经红外光谱、核磁共振谱、质谱确认结构.此法合成虽然收率不太高,但利用此法可更简便地一步合成出羟基查尔酮类衍生物.     

Synthesis of New Spin Labeled Derivatives of Podophyllotoxin as Potential Anticancer Agents

AsaresultOfthedevlOPmentOfetOPOSide(VPl6)andteaiPOSide(VM-26)asanticancertw,thesendSynheticanalOgUsOfthenaturailyoccuning~OtOkin(l)havebomuchrenewedinterestinrecentyears.Inourprevioushees",wefOundthatanumterOfhitroXy1opnltheledderivativesOf~yllOtoxinhadsignfficantanticancerAnvitywithInareddecreaseintoxidtycomParedwiththeParentcompoundlandVPl6.AseriesofSPinldeledderibovesOfthio-TEPA,'`,nitrosourea',andruboInyin8werealsoreportedtohavSUPeriorpharmaCOledtalpmprtiestotheirparentco…     

Synthesis and Characterization of Cyclotriphosphazenes Bearing Chalcones Derivatives

A series of new cyclotriphosphazenes bearing chalcones derivatives, N₃P₃Cl₅[OC₆H₄ CH=CHC(O)C₆H₄OC_nH_2n+1] and N₃P₃[OC₆H₄CH=CHC(O)—C₆H₄OC_nH_2n+1]₆, has been synthesized. A convenient synthetic method was performed from the reaction of hexachlorocyclotriphosphazenes with one and six equivalents of (E)-3-(4-(alkyloxy)phenyl)-1-(4-hydroxyphenyl)prop-2-en-1-one (2a–c). The compounds differ in the length of alkyl groups, C_nH_2n+1, where n = 10, 12, and 14, respectively. All the products were obtained in high yields. The structures of the synthesized compounds were defined by elemental analysis, IR, ¹H, ¹³C, and ³¹P NMR.     

The Synthesis of Podophyllotoxin Derivatives with Macrocyclic Dilactone

Podophyllotoxin1andmanyofitsderivatives,includingC-2epimer,picropodophyllin2.areantimitoticagents'.Thesemi'syntheticderivativesofIetoposide(VP-16-213)andteniposide(VM-26)areinclinicaluseasanti-canceragents'.SomeanaloguesofIwithamodifiedlactoneringhavebeensynthesizedandfoundtobestillantimitotic'.therebyindicatingthatthelactoneringisnotrequiredforantimitoticactivityin1.Anjanamurthyetap.ha.esynthesizedaderivativebyenlargingthefive-memberedlactoneringinItoasix-memberedone.Sincethen.however.nos…     

Synthesis of substituted benzene derivatives by homo- and hetero-coupling of 2-bromobenzaldehyde and bromovinylaldehydes followed by McMurry coupling

A convenient synthetic approach to substituted benzene derivatives by modified Ullmann cross-coupling of 2-bromobenzaldehyde and bromovinylaldehydes followed by intramolecular McMurry coupling has been developed.     

Design,Synthesis and Antitubulin Activity of Novel Podophyllotoxin Derivatives as Potent Anticancer Agent

Twenty novel podophyllotoxin derivatives(1―20) were designed and synthesized. The anti-proliferation activities of these compounds were evaluated against three human cancer cell lines(HepG2, Calu-1 and MCF-7) using podophyllotoxin and Combretastatin A4(CA-4) as positive controls. Among all the compounds, compound 2 displayed more significant anti-proliferation activities against MCF-7 and Calu-1 cell lines and showed lower toxicity towards non-cancer cells. Furthermore, the cell cycle and apoptosis analysis results revealed that compound 2 can cause cell arrest at G2/M phase, leading to cancer cell apoptosis. Meanwhile, it can also reduce the adhesive ability of Calu-1 cells to fibronectin and laminin. The docking simulation results demonstrated that compound 10 can nicely bind to the colchicine site of tubulin. The podophyllotoxin derivatives are worthy to be further investigated to obtain more potent anti-cancer drugs.     

The use of McMurry coupling for the synthesis of indolophanes and cis-stilbenophanes

Treatment of 2 equiv of indole-3-aldehyde with o, m, p-xylyl, 2,5-dimethoxy-p-xylyl dibromides and 4,4′-bis(bromomethyl)-1,1′-biphenyl gave the bisalkylated products, which underwent McMurry coupling with low valent titanium to give indolophanes. Various cis-stilbenophanes with m-terphenyl building blocks were also synthesized by application of the McMurry coupling technique.     

Synthesis and properties of a graphene-like macrocycle based on tetraphenylethene

In this work, tetraphenylethene macrocycles are selectively synthesized in one step from McMurry coupling reaction of 1,1-bis(4-phenylcarbonyl)-2,2-diphenylethene in 45% overall yield. A more planar cyclized compound can be obtained by oxidization of tetraphenylethene macrocycles with iron (III) chloride in nitromethane. Their unusual optical properties and electrical properties are explored. The measured mobilities are 0.7022 and 0.0055 cm² V⁻¹ s⁻¹, respectively. The decomposition temperatures are also measured by thermal gravimetric analysis as, respectively 342 °C and 455 °C, indicating good thermal stabilities. The understanding of the structure and properties will benefit to the chemical synthesis of graphene.     

Stereoselective Synthesis of 1-Aminocyclopropanecarboxylic Acid Derivatives via Ylide Cyclopropanation of Dehydroamino Acid Derivatives

1‐Aminocyclopropanecarboxylic acid derivatives are synthesized from readily available dehydroamino acid derivatives via sulfur ylide. A range of different ylides are employed and the corresponding aminocyclopropanes are afforded with reasonable diastereoselection in good yields.     

Synthesis of (+)-Septicine Using Intramolecular McMurry Coupling: A Chiron Approach

Total synthesis of secophenanthroindolizidine alkaloid (+)-septicine 1 was accomplished using the McMurry coupling for the construction of indolizidine ring, using L-glutamicacid as chiral source.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.     

有机碲Ylide反应Ⅻ用碲Ylide合成双环丙烷衍生物

由相应的碲盐生成的某些碲ylide,能顺利地和1,4-双(3-取代苯基-3-酮-1-丙烯基)苯,1,5-二取代苯基-1,4-戊二烯-3-酮反应生成双环丙烷衍生物,反应具有高立体选择性,产率为61.8-88.8％。     

抗癌活性鬼臼毒素衍生物的合成与构效关系研究

合成了１３个新的鬼臼毒素衍生物５－１７，经元素分析ＩＲ，ＭＳ，ＥＳＲ和＾１ＨＮＭＲ分析确证了其组成和结构，并对它们进行了抑制小鼠淋巴白血病Ｐ３８８和人胃腺癌ＳＧＣ－７９０１细胞体外筛选，发现新化合物５，７－１０对两种瘤株均有显著抑制活性，４′－Ｏ－去甲基鬼臼毒素５，１０－１３的抗癌活性大于相应的４′－甲氧基类似物６，１４－１７，用“－Ｏ－”桥取代Ｃ－４位的“－ＮＨ－”桥可导致抗癌活性降低。     

低价钛在有机合成中的应用新进展

主要综述了近年来低价钛诱导的McMurry反应在有机合成中的应用新进展.     

Tandem one-pot intra- and inter-molecular McMurry coupling for the synthesis of bisindolostilbenophanes

Treatment of 3 equiv of indole-3-aldehyde with 1,3,5-trimethyl-2,4,6-tris(bromomethyl)benzene and 1,3,5-tris(bromomethyl)benzene gave the tris-alkylated products, which underwent both intra- and inter-molecular McMurry coupling in one-pot with low valent titanium to give indole-based stilbenophanes.     

Fluorinated Isocyanates and Their Derivatives as Intermediates for Biologically Active Compounds

Fluorinated aromatic isocyanates are valuable intermediates for the production of herbicides and insecticides. Unexpected rearrangements during the synthesis of 2-(trifluoromethyl)phenyl isocyanates provide an entry to N-trifluoromethylaminobenzoyl fluorides, a novel class of compounds having fungicidal properties. Carbamoyl fluorides, the products of HF addition to isocyanates, undergo ready sulfenylation. Use of these intermediates for the synthesis of N-sulfenylcarbamate insecticides led to the discovery of the new principle of detoxification of carbamates by sulfenylation.