由(E)-β-碘代烯基砜和末端炔合成多取代的1,3-烯炔

通过(E)-b-碘代烯基砜与末端炔的Sonogashira偶联反应,以中等到良好的产率合成了磺酰基取代的1,3-烯炔。在NiCl2(PPh3)2催化下,产物与格氏试剂发生脱磺酰基偶联反应,磺酰基被进一步转化为不同的取代基。     

A facile stereospecific synthesis of （Z）-2-sulfonyl-substituted 1,3-enynes via Sonogashira coupling of （E）-α-iodovinyl sulfones with 1-alkynes

(E)-a-Iodovinyl sulfones 1 underwent the Sonogashira coupling reactions with terminal alkynes 2 in piperidine at room temperature in the presence of 5 mol% of Pd(PPh3)4 and 10 mol% of CuI to stereospecifically afford the corresponding (Z)-2- sulfonyl-substituted 1,3-enynes 3 in high yields.     

3-甲基-5-苯砜基-3E-戊烯-1-醇的立体专一性合成

3-甲基-5-苯砜基-3E-戊烯-1-醇(1)是合成某些萜类化合物的重要中间体.它具有反式烯丙基苯砜基双键.Julia等曾报道用含砜基的环丙基醇的开环重排反应来实现这类化合物的立体选择性合成,但其开环前体不易得到.本文以4-羟基-2-丁酮(2)为起始原料,经4步反应立体专一性地合成了标题化合物1.合成路线短、操作简便、易于大量制备.合成路线用方程式表示如下:     

三组分一锅法合成3-(2-喹啉基)薁甲酸甲酯衍生物

在质子酸作用下, 以1-甲酰基薁-3-甲酸甲酯、芳香胺和脂肪醛为原料, 三组分一锅法合成了一系列3-(2-喹啉基)薁甲酸甲酯衍生物. 该反应收率良好、操作简单、条件温和. 产物的结构通过红外光谱、核磁共振谱和元素分析证实, 同时给出了该反应可能的反应机理.     

Stereoselective Synthesis of 1,3-Enynylstannanes via Palladium Catalyzed Cross-Coupling Reactions of （Z）-α-Bromovinylstannanes

Based on the different reactivity of stannyl and bromo groups, (Z)-α-bromovinylstannanes can undergo the cross-coupling reaction with alkynyl Grignard reagents in the presence of tetrakis(triphenylphosphine)palladium(0) catalyst in THF at room temperature to afford stereoselectively 1,3-enynylstannanes in good yields.     

新型N^C^N三齿配体1,3-二(2′-嘧啶基)-5-甲氧基苯的合成

以1,1,3,3-四甲氧基丙烷为起始原料,经Stille偶联等五步反应合成了新型N^C^N三齿配体——1,3-二(2′-嘧啶基)-5-甲氧基苯,其结构经1H NMR,13C NMR和EI-MS表征.     

(Z)-3-三苯基锡基-1,1-二苯基烯丙醇的合成、晶体结构和性质研究

合成并表征了5种新的有机锡化合物.测定了(Z)-3-三苯基锡基-1,1-二苯基烯丙醇的晶体结构.晶体属于P2₁/n空间群,晶胞参数α=1.2357(3)nm,6=0.9874(2)nm,c=2.2081(2)nm,β=95.23(3).,z-4.分子结构是以锡为中心的畸变四面体构型,双键为顺式构型.并对其性质进行了研究.     

1-[(Z)-2-(-苯基二溴化锡基)乙烯基]环戊醇的合成及晶体结构

通过１［（Ｚ）２（三苯基锡基）乙烯基］环戊醇与Ｂｒ２反应制得了新化合物１［（Ｚ）２（苯基二溴化锡基）乙烯基］环戊醇．通过元素分析、锡含量测定、ＩＲ、１ＨＮＭＲ对其进行了表征并用Ｘ射线衍射法测得了所合成化合物的晶体结构．该化合物属正交晶系，Ｐ２１２１２１空间群，晶胞参数：ａ＝０８６７５（４）ｎｍ，ｂ＝１２５２３（７）ｎｍ，ｃ＝１４００９（８）ｎｍ；Ｚ＝４，Ｖ＝１５２１９ｎｍ３，Ｄｃ＝２．３９ｃｍ３，ｕ＝２３．７２ｃｍ－１．结构分析表明，标题化合物分子为畸变的三角双锥构架，双键的两个氢取顺式结构，分子中Ｏ与Ｓｎ配位，形成五元螯合环结构     

2-肟基丙二腈与羟胺反应合成1,3-二氨基-1,2,3-三肟基丙烷反应动力学研究

2-肟基丙二腈与羟胺反应合成1,3-二氨基-1,2,3-三肟基丙烷是合成呋咱衍生物的关键步骤. 利用紫外光谱法对该反应的动力学进行了研究. 实验结果表明反应为二级反应, 分反应级数各为一级. 10 ℃时, 该反应速率常数为0.0679 L•mol^－1•min^－1|提高2-肟基丙二腈、羟胺的浓度和反应温度, 可以加快反应速率.     

各种烯基锆化合物的合成及其在立体选择性合成二(三)取代的烯烃中的应用

烯基锆化合物及硒基烯基锆化合物、锡基烯基锆化合物、磺酰基烯基锆化合物、亚磺酰基烯基锆化合物、硅基烯基锆化合物等金属或杂原子取代的烯基锆化合物 ,可通过锆氢化反应高产率和高选择性地制得 .这些试剂可与各种亲电试剂反应立体选择性地合成二取代或三取代的烯烃化合物     

Tandem One‐pot Synthesis of Polysubstituted 1,3‐Thiazine Derivatives

A tandem one‐pot synthesis of polysubstituted 1,3‐thiazines has been developed by reacting with cyanoacetamide and isothiocyanate derivatives to give rise to 2‐cyano‐3‐mercaptoacrylamides, which are trapped in situ by various aldehydes or diversely substituted ketones through intermolecular cyclization, providing polysubstituted 1,3‐thiazine derivatives in short reaction times with good to excellent yields. The salient features of this novel protocol are operational simplicity, accessing the desired products from the readily available starting materials and easy of product isolation and may find wide spread applications in medicinal chemistry.     

A one‐pot,stereoselective synthesis of 2‐ethoxycarbonyl‐substituted 1,3‐dienes and 1,3‐enynes by hydrostannylation–Stille tandem reaction of tributyltin hydride with alkynyl esters and alkenyl or alkynyl halides

2‐Ethoxycarbonyl‐substituted 1,3‐dienes and 1,3‐enynes can be stereoselectively synthesized in one pot under mild conditions, in good yields, by the palladium‐catalyzed hydrostannylation of alkynyl esters, followed by Stille coupling with alkenyl or alkynyl halides, respectively. Copyright © 2009 John Wiley & Sons, Ltd.     

Stereoselective Synthesis of cis‐β‐Methyl‐ and Phenyl‐Substituted Alkenylboronates by Platinum‐Catalyzed Dehydrogenative Borylation

Changing places : Intramolecular B(pin)/H exchange took place in the presence of a platinum–phosphane catalyst, giving synthetically useful cis‐β‐methyl‐substituted alkenylboronates stereoselectively (see scheme; B(pin)=4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolan‐2‐yl).

     

一种经(E)-α-碘代烯基砜的钯催化交叉偶联反应立体选择合成(1Z,3E)-2-芳砜基取代的1,3-二烯的新方法

（E）-α-Stannylvinyl phenyl（or p-tolyl）sulfones underwent an iododestannylation reaction to afford （E）-α-iodovinyl phenyl（or p-tolyl）sulfones 1, which reacted with （E）-alkenylzirconium（IV） complexes 2 produced in situ by hydrozirconation of terminal alkynes in the presence of a Pd（PPh3）4 catalyst to afford stereoselectively （1Z,3E）-2- phenyl（or p-tolyl）sulfonyl-substituted 1,3-dienes 3 in good yields.     

One‐pot Two‐Step Cycloaddition Reaction for Convenient Synthesis of Polycyclic Spirooxindole‐fused [1,3]Oxazines

The novel spirooxindoline fused [1,3]oxazines were efficiently synthesized from Diels‐Alder reaction of N‐arylmaleimides with 1,2‐dihydro‐2‐oxospiro[3H‐indole‐3,2′‐[2H,9aH‐pyrido[2,1‐b][1,3]oxazines], which were generated in situ from three‐component reactions of substituted pyridines and isatins with methyl propiolate, or dimethyl acetylenedicarboxylate. The stereochemistry of the products was clearly clarified by the analysis of ¹H NMR data and single crystal structures of the obtained polycyclic compounds.     

（E）-α-Bromovinylselenides as Convenient Precursors for Stereose-lective Synthesis of Trisubstituted Alkenes

Based on the different reactivity of selanyl and bromo groups,(E)-α-bromovinylselenides can undergo sequential cross coupling reactions with nucleophiles in the presence of transition metal complexes to form two carbon-carbon bonds in the same olefinic carbon leading to trisubstituted alkenes stereoselectively in good yields.     

Tandem Reaction of Deprotonation-Oxidation-Wittig Reaction: Stereoselective Synthesis of (E)-α,β-Unsaturated Enoates

Ｓｉｎｃｅｉｔｓｄｉｓｃｏｖｅｒｙ ,Ｗｉｔｔｉｇｒｅａｃｔｉｏｎｈａｓｂｅｃｏｍｅｏｎｅｏｆｐｒｉｍａｒｙｍｅｔｈｏｄｓｆｏｒｔｈｅｆｏｒｍａｔｉｏｎｏｆｃａｒｂｏｎ ｃａｒｂｏｎｄｏｕｂｌｅｂｏｎｄｓａｎｄｂｅｅｎｗｉｄｅｌｙｕｓｅｄｉｎｔｈｅｓｙｎｔｈｅｓｉｓｏｆｎａｔｕｒａｌｐｒｏｄｕｃｔｓ .1,2 Ｒｅｃｅｎｔｌｙ ,ｉｔｗａｓｆｏｕｎｄｔｈａｔｐｒｉｍａｒｙａｌｃｏｈｏｌｓｃａｎｕｎｄｅｒｇｏｔｈｅｔａｎｄｅｍｒｅａｃｔｉｏｎｏｆｏｘｉｄａｔｉｏｎ Ｗｉｔｔｉｇｒｅａｃｔｉｏｎｗｉｔｈｐｈｏｓ…