Garcinol及其新衍生物8-Allyl Garcinol对人口腔鳞癌细胞的抑制作用对比研究

目的比较Garcinol及其新衍生物8-Allyl Garcinol对人口腔鳞癌细胞系SCC15生物学行为的影响。方法培养人口腔鳞癌细胞系SCC15,采用不同浓度的Garcinol、8-Allyl Garcinol处理细胞后,通过MTT法检测对细胞增殖的影响、克隆形成实验检测对细胞克隆形成能力的影响、划痕实验检测对细胞迁移能力的影响、Annexin V-FITC/PI双染色流式细胞术检测对细胞凋亡的影响,比较Garcinol和8-Allyl Garcinol对人口腔鳞癌细胞生物学行为影响的差异。结果 Garcinol和8-Allyl Garcinol均能抑制人口腔鳞癌细胞SCC15的增殖、克隆形成及迁移能力,并促进细胞的凋亡,呈一定的时间和剂量依赖性。其中,8-Allyl Garcinol对细胞增殖及细胞克隆形成的抑制作用优于Garcinol(P <0. 01),但促进细胞凋亡效果较Garcinol弱(P <0. 05),对细胞迁移能力的抑制作用二者未见统计学差异(P> 0. 05)。结论 8-Allyl Garcinol对人口腔鳞癌细胞SCC15具有显著的抑制作用,但作用效果和机制与Garcinol有一定差异。

REDUCING NONSELECTIVE PROTEIN ADSORPTION AND CELL ADHESION ON POLYACRYLONITRILE FILMS BY COPOLYMERIZATION OF ACRYLONITRILE WITH α-ALLYL GLUCOSIDE

In this work, the surface properties of novel sugar-containing polymers, α-allyl glucoside (AG)/acrylonitrile (AN)copolymers, were studied by contact angle, protein adsorption and cell adhesion measurements. It was found that the contactangle of the copolymer films decreased from 68° to 30° with the increase of AG content in the copolymer. The adsorptionamount of bovine serum albumin (BSA) and the adhesive macrophage onto the film surface also decreased significantly withincreasing α-allyl glucoside content from 0 to 42 wt% in the copolymer. These preliminary results reveal that both thehydrophilicity and the biocompatibility of polyacrylonitrile-based membranes could be improved by copolymerizin gacrylonitrile with vinyl carbohydrates.

Remarkable rate acceleration of SmI3-mediated iodination of acetates of Baylis-Hillman adducts in ionic liquid: facile synthesis of (Z)-allyl iodides

Stereoselective transformation of Baylis-Hillman acetates I into corresponding （Z）-allyl iodides 2 has been achieved by treatment of I with samarium triiodide in THF. Remarkable rate acceleration of samarium triiodide-mediated iodination of 1 was found when ionic liquid 1-n-butyl-3-methyl-imidazolium tetrafluroborate （[bmim]BF4） was used as reaction media in stead of THF. This novel approach proceeds readily at 50 ℃ within a few minutes to afford （Z）-allyl iodides 2 in excellent yields. A mechanism involving stereoselective iodination of the acetates of Baylis-Hillman adducts by samarium triiodide is described, in which a six-membered ring transition state played a key role in the stereoselective formation of 2.

A convenient and stereoselective synthesis of (Z)-allyl selenides via Sm/TMSCl system-promoted coupling of Baylis-Hillman adducts with diselenides

A simple and convenient procedure for stercoselective synthesis of （Z）-allyl selenides has been developed by a one-pot reaction of diselenides with Baylis-Hillman adducts in the presence of samarium metal-trimethylsilyl chloride under mild conditions. Presumably, the diselenides are cleaved by Sm/TMSCI system to form selemde anions, which then undergo SN2＇ substitution of Baylis-Hillman adducts to produce the （Z）-allyl selenides.

Solid-phase synthesis of (Z)-allyl iodides from 3-acetoxy-2-methylene-alkanoates with recyclable polymer-supported selenium bromide

Reaction of polystyrene-supported lithium selenide with 3-acetoxy-2-methylene-alkanoates afforded the corresponding allyl selenide resins and subsequent cleavage from the polymer by treating with methyl iodide to furnish （Z）-allyl iodides in good yields and high purities. The polymeric selenium reagent can be regenerated and reused. So it is a environmentally benign reagent.

A General Protocol toward Oxindoles Bearing C3-Allylic Quaternary Stereocenter via Domino Reaction:A Concise Synthesis of Heterocycle-Fused Indoline Alkaloids

An efficiently catalytic method toward the synthesis of indolin-2-ones featuring an allylic derived C3-quaternary stereocenter via an intramolecular Heck cyclization/Suzuki coupling of N-substituted-N-(2-bromophenyl)acrylamides and organoboron reagents was successfully developed by using a 1,3-bis(2,6-diisopropylphenyl)acenaphthoimidazol-2-ylidene(AnIPr)-ligated oxazoline palladacycle.It enabled a very broad substrate scope tolerating different functional groups,electronic properties and steric bulkiness.Notably,it revealed a great potential to build diverse heterocycle-fused indoline alkaloids via the same intermediate 3-allyl-1,3-dimethylindolin-2-one.

α-烯丙基甘油醚的合成新方法

在路易斯酸催化下，烯丙醇和环氧氯丙烷经加成、环化和水解后得到标题化合物，该法比文献报道的甘油－氯丙烯法产率提高约１０％。

丙烯酸酯偶联剂在丙烯酸酯改性聚氨酯杂化材料中的反应活性

合成烯丙基甘油醚(AG)作为一种新型双羟基偶联剂用于聚氨酯(PU)与丙烯酸酯聚合物(PAC)的改性材料。采用核磁共振、红外光谱和气相色谱等对其进行表征。研究偶联剂AG和HEA与PU预聚体和丙烯酸酯单体的反应性。实验结果表明:随着偶联剂(AG和HEA)与PU反应温度的升高,异氰酸酯(NCO)的转化率逐渐增加;使用AG为偶联剂时,PU和AC未发生接枝反应;使用HEA为偶联剂时,明显发生了预期的接枝反应。当n(HEA)∶n(NCO)<1时,随HEA用量增加,PU与AC的接枝率逐渐增加;当n(HEA)∶n(NCO)>1时,继续增加HEA用量PU接枝率变化不大。

Recent advances of Pd-π-allyl zwitterions in cycloaddition reactions

Palladium-catalyzed cycloaddition reactions via Pd-π-allyl zwitterions have been established as significant synthetic transformations to enable numerous carbon-or heterocycles compounds that are key constituents of various biologically active natural products and pharmaceuticals.In addition to the well-known Pd-π-allyl zwitterions,including palladium-trimethylenemethane and Pd-1,3/1,4-zwitterions,chemists have recently discovered new applications of several long ago reported but less-studied Pd-π-allyl zwitterions,which can straightforwardly and efficiently construct novel cyclic architectures.Meanwhile,some impressive newly designed zwitterions have been also developed.Those zwitterions are diverse and can serve as transient and highly reactive intermediates for the subsequent cyclization with various acceptors.In this review,we highlight recent advances in applications of these two types of zwitterions in the synthesis of complex polycyclics and medium-sized cyclic compounds.

Biobased Aromatic-Aliphatic Polyols by Thiol-Ene Reactions of Propoxylated Mercaptanized Cardanol

Aromatic-aliphatic polyols were obtained previously from the thiol-ene reactions of propoxylated cardanol with hydroxyalkyl mercaptans;these aromatic-aliphatic polyols were then utilized in the preparation of rigid polyurethane foams with excellent properties.The current work describes a variant of cardanol polyol synthesis by thiol-ene reactions in three steps.The first step is propoxylation of cardanol by reacting cardanol with propylene oxide;the second step is mercaptanization of propoxylated cardanol by reacting double bonds with hydrogen sulfide;and the third step involves the addition of the thiol groups of mercaptanized propoxylated cardanol to the double bonds of allyl alcohol,glycerol-1-allyl ether,and trimethylolpropane allyl ether.Thus,obtained polyols were characterized by standard analytical methods.Rigid polyurethane foams prepared from these polyols show promising physical-mechanical properties.The rigid polyurethane foams can be used for various applications such as thermo-insulation of freezers,storage tanks and pipes for food and chemical industries,wood substitutes and flotation materials.

POLYMERIZATION MECHANISM OF DIENES WITH HOMOGENEOUS RARE EARTH CATALYSTS

The reaction mechanisms of diene polymerization with homogeneous rare earth catalyst are studied by means of the spectra of ~1H-NMR, one-and two-dimensions ^(13)C-NMR. Based on the data of above NMR spectra, it is proposed that the polymerization reaction proceeds according to the following mechanism: η~4-diene (cis-trans-)and η~3-allyl (syn-anti-).

Access to Enantioenriched Allylic Alcohols via Peptide-Mimic Phosphonium Salt-Catalyzed Asymmetric Aerobic Hydroxylation

The development of catalytic asymmetric methods that enable access to value-added functionalities or structures,exemplified by allylic alcohols,is a highly interesting yet challenging topic from both academic and industrial perspectives.However,before recent advances in chemical catalysis,there were scarce protocols toward constructing enantioenriched tertiary allylic alcohol scaffolds.In this context,peptide-mimic phosphonium salts were found to be highly efficient in catalytic asymmetricα-hydroxylation ofα,β-unsaturated and/orβ,Y-unsaturated compounds with satisfactory regio-and stereochemical outcomes(up to 97%yield and 95%ee).This methodology tolerates a broad array of substrates and thus provides an expeditious and unified platform for the assembly of enantioenriched tertiary allylic alcohols by avoiding the use of additional reductants and expensive metal catalysts.Furthermore,the power of this protocol is enlarged by simple conditions and the use of air as a source of hydroxyl functionality.

Palladium-Catalyzed Selective Syntheses of 2,3-Allenyl Amines via Double Functionalization Coupling of 2-Alkynyl-1,4-diol Dicarbonates

Comprehensive Summary 2,3-Allenyl amines have shown wide applicability in biomedical and synthetic applications.Due to their enormous potential for applications,researchers have been dedicated to the development of methods for synthesizing 2,3-allenyl amines.Herein,a palladium-catalyzed three-component reaction of 2-alkynyl-1,4-diol dicarbonates,organoboronic acids,and nitrogen nucleophiles forming 2,3-allenyl amines with excellent regio-and chemo-selectivity has been developed.Substrate compatibility and synthetic applications have been demonstrated.Control experiments supported a mechanism involving 1,2,3-triene-Pd species and methylene-π-allyl palladium species.

Rapid formation of β-allyl substituted isotetronic acid derivatives via Claisen rearrangement using a microfludic device

The thermal Claisen rearrangement of O-allyl substituted isotetronic acids 1 was successfully carried out within a glass microreactor operated with temperature at 150℃and a flow rate of 1 mL/h.The strategy provides an efficient alternative way toβ-allyl substituted isotetronic acid derivatives 2 in high yields with much accelerated reaction speed.

Primary-Tertiary Diamine/Brønsted Acid Catalyzed α-Allylation of Carbonyl Compounds with Allylic Alcohols

A simple and directα-allylic alkylation of unmodified aldehydes with allylic alcohols catalyzed by primary amine/Brønsted acid has been developed.The N,N-dimethylethylenediamine/TfOH was identified as the optimal catalyst to promote this transformation via an enamine process in high yields(up to 88%)and with good diastereoselectivities(up to 9∶1).