Ferric chloride-catalyzed decarboxylative alkylation of β-keto acids with benzylic alcohols

β-Keto acids are unstable to heat,acids,and bases,and have rarely been employed as carbon nucleophiles for the formation of carbon-carbon bonds.In this context,an efficient decarboxylative alkylation reaction of β-keto acids with benzylic alcohols has been developed,for the first time,through sequential cleavage of carbon-oxygen and carbon-carbon bonds.In the presence of 10 mol% of ferric chloride,a range of β-keto acids smoothly undergo decarboxylative alkylation with benzylic alcohols to give structurally diverse unsymmetric ketones in moderate to excellent yields and with extremely high regioselectivity.Preliminary mechanistic studies indicate that the reaction proceeds through an SN1 alkylation followed by decarboxylation.     

Biosynthesis of 1-alkenes in the defensive secretions ofTribolium confusum (Tenebrionidae); stereochemical implications

Summary The terminally unsaturated hydrocarbons of the defensive secretion ofTribolium confusum are biosynthesized from fatty acids by oxidative decarboxylation. The process involves an enantiospecific cleavage of the C–H bond of thepro-(S) C(3)–H atom and simultaneous decarboxylation of the acid into an 1-alkene and carbon dioxide via ananti-periplanar transition state geometry (anti-elimination). The stereochemistry of this biotranformation is identical in all respects with the same reaction in higher plants. The mechanism seems to be of general importance for the biosynthesis of many vinylic substructures of natural products from oxygen-containing precursors.     

3,5—二甲氧基苯甲醛的合成

以对硝基甲苯为原料,经化还原,溴化,重氮化去氨基,甲氧基化反应制得到３,５－二甲氧苯甲醛,总收率在５１％以上。     

盐水对未熟生油岩中脂肪酸催化脱羧生烃的影响

选择十八烷酸为模型化合物 ,以辽河、江汉两种未熟生油岩为样品 ,在模拟地质条件 (10MPa、16 0℃ )下考察了浓度为 10 %的NaCl,KCl,MgCl2 ,Na2 SO4 等 4种盐水及不同 pH值的NaCl盐水对未熟生油岩中脂肪酸矿物催化脱羧生烃的影响。结果表明 ,对于辽河生油岩样 ,Na2 SO4 作用下的十八烷酸的矿物催化脱羧率最高 ,其次为KCl,NaCl,MgCl2 。对于江汉生油岩样 ,KCl作用下的十八烷酸矿物催化脱羧率最高 ,其次为NaCl,Na2 SO4 ,MgCl2 。pH值对十八烷酸矿物催化脱羧生烃有一定的影响 ,当pH =8时 ,十八烷酸脱羧率最高。这说明 ,在 pH =8附近的碱性条件下 ,未熟生油岩对十八烷酸的脱羧生烃催化活性最大。模拟未熟生油岩的古沉积环境 ,对存在地层混合水时未熟生油岩对十八烷酸的脱羧生烃影响的考察结果表明 ,在 pH =8时 ,十八烷酸脱羧率最高 ,与单一盐类的影响规律相同     

Oxidative photochemical decarboxylation of zaragozic acid A

A unique decomposition reaction of the novel squalene synthase inhibitors called zaragozic acids has been studied. Under very mild conditions, e.g. by merely exposing their solutions to air and visible light at ambient temperature, these compounds, characterized by the 2,8-dioxabicyclo[3.2.1]octane-4,6,7-trihydroxy-3,4,5-tricarboxylic acid core, rapidly decompose. As relatively stable intermediates in the cascade of decomposition, the biologically active 2,8-dioxabicyclo[3.2.1]octane-6,7-dihydroxy-4-keto-5-caroxylic acid (or 3,4-decarboxy-4-dehydro) derivatives of these compounds have been isolated in ca. 20% yield. Derivatization on the highly reactive 4-carbonyl group yields stable derivatives, several of which are potent inhibitors of squalene synthase. Further decomposition results in the elimination of C3 and C4 atoms and the carboxylic acid on C5, the oxidation of C5 to carboxylic acid and the liberation of the oxo group on C1. Specific results obtained with zaragozic acid A, a key representative of the family of these potent cholesterol-lowering agents, are presented in this study.     

羧酸与过渡金属或碳酸盐形成的共轭体系的EHMO计算

利用扩展休克尔分子轨道(EHMO)法计算了羧酸与金属或碳酸盐形成的共轭体系的电荷密度(ED)、键级(BO)、自由价(FV),研究了从Ca到Zn等金属及其碳酸盐等构成的不同共轭体系对羧酸低温催化脱羧反应难易程度,比较了不同共轭体系对羧酸低温催化脱羧反应活化能的影响。结果表明：金属及其碳酸盐促进羧酸脱羧,过渡金属及其碳酸盐更利于低温脱羧反应的进行,尤其以FeCO3 催化效果最优,且碳酸盐的催化活性大于金属。     

反式肉桂酸负离子模式质谱裂解脱羧机理的 计算研究

采用密度泛函理论方法RB3LYP/++6-311G（d,p）对反式肉桂酸负离子模式下质谱裂 解脱羧机理进行了理论研究。计算结果表明,当外加能量得以满足时,反式肉桂酸可实现羧基化 合物质谱不同的脱羧机制。反式肉桂酸质谱消除CO2途径按去质子分子结构中的氢所经的状态可 归为4类,即：氢均保持在原位碳上脱羧,侧链上β氢迁移到苯环后脱羧,β氢迁移至α碳上重排后 脱羧,β氢与羧基氧结合经重排后脱羧。反式肉桂酸质谱裂解脱羧共计有5种可能途径,产生4种 脱羧产物。脱羧的途径中,以去质子分子的氢保持在原位碳上并经1个过渡态的脱羧最具优势。 脱羧产物中,以苯乙烯负离子能量最低、最为稳定。     

丙二酸发生羟醛缩合时的二次脱羧反应

 丙二酸与对羟基苯甲醛及对羟基间甲氧基苯甲醛反应会发生第二步脱羧,生成对羟基苯乙烯及对羟基间甲氧基苯乙烯,是一种形成对羟基苯乙烯的新方法.而间羟基及其它烷氧基取代苯甲醛则不能发生此反应,讨论了对羟基苯甲醛与丙二酸发生脱羧反应的电子效应.     

苯五酸原位脱羧形成锌配合物的水热合成和结构研究

水热反应条件下，Zn（NO3）2·4H20、苯五酸和2，2＇-联吡啶反应生成一个新颖的配位聚合物[zn2（1，2，3，5-htc）（2，2’-bpy）2（H2o）]n·0．5nH2O（1，2，3，5-btc=1，2，3，5-苯四酸），通过x射线单晶衍射分析、元素分析和红外光谱对它进行了表征．配合物的结构是由二维配位层通过π-π堆积和氢键作用形成的三维超分子结构．采取μ4桥连配位模式的1，2，3，5一苯四酸是在高温水热碱性条件下由原来的苯五酸通过原位脱羧反应而形成．CCDC：790205．     

Catalytic decarboxylation of fatty acid by iron-containing minerals in immature oil source rocks at low temperature

The catalytic activities of seven immature source rocks in China on fatty acid decar-boxylation for generating hydrocarbons have been evaluated by determinating the CO2 content from decarboxylation reaction of stearic acid. It has been found that the catalytic activities of immature source rocks mainly depend on the structure type of the minerals. In general, the catalytic activities of carbonates are higher than those of clays at low temperature. The higher its iron content, the higher the catalytic activity of carbonate.