钯催化合成2-(2,4-二氟苯基)吡啶

以Pd(OAc)2为主催化剂,PPh3为配体,2-溴(氯)吡啶和2,4-二氟苯硼酸通过Suzuki偶联反应合成了2-(2,4-二氟苯基)吡啶,产率＞90%,其结构经1H NMR,19F NMR和IR确证.     

一锅法Kumada偶联反应合成烷基吡啶化合物

以溴代吡啶为原料,用简单结构的镍化合物(Py4NiCl2)作为催化剂,经过一锅法Kumada偶联反应合成一系列甲基、烯丙基或苄基取代的吡啶化合物,收率在中等以上.     

二价钯催化的α或β联烯胺与烯丙基溴的偶联环化反应的研究

官能团化的联烯在过渡金属钯物种催化下的偶联环化反应作为一种有效的合成含氮、氧杂环的方法已经受到越来越多的重视[1].但是,联烯胺与烯丙基溴的偶联环化反应还没有被深入的研究过.我们组对钯催化下联烯醇与烯丙基溴的反应进行了一些研究[2],并基于此进行了联烯胺与烯丙基溴的偶联环化反应的研究.我们经过研究发现,可以通过二价钯催化,高效地经由α或β联烯胺与烯丙基溴的反应得到2,5-二氢吡咯或1,2,3,6-四氢吡啶类化合物,并且经过研究证明反应是通过二价钯的催化循环历程进行的.     

一种新型多吡啶钌配合物的合成及其太阳光谱响应特性

以二茂铁和2-吡啶甲酰胺为原料,经偶联、氧化、溴乙酰化及环合反应制备了一种新型的二茂铁噻唑衍生物4-二茂铁-2-(2-吡啶)基噻唑(2-FPT);以2-FPT为第一配体,2,2'-联吡啶-4,4'-二甲酸(dcbpy)为第二配体,与二异苯丙基氯化钌进行配位,合成了一种新型的光敏化染料Ru(dcbpy)2(2-FPT)(...     

新型CCR5拮抗剂——N-【1-{5-溴-2-[(4-氯苄基)氧基]苄基}-4-哌啶基】-N-乙基吡啶甲酰胺的合成

以5-溴水杨醛和4-氯苄氯为原料,通过消去、还原及溴化反应制得中间体4-溴-2-溴甲基-1-[(4-溴苄基)氧]苯(3);哌啶-4-酮经Boc保护、还原等4步反应制得中间体N-乙基-N-(4-哌啶基)吡啶甲酰胺(7);3与7通过消去反应合成了一种新型CCR5拮抗剂——N-【1-{5-溴-2-[(4-氯苄基)氧基]苄基}-4-哌啶基】-N-乙基吡啶甲酰胺,其结构经1H NMR,13C NMR和ESI-MS表征。     

钯催化下吡唑与2,6-二溴吡啶的偶联反应

 在相对温和的反应条件以及PPh3和KOtBu存在的情况下,Pd(OAc)2催化吡唑与2,6-二溴吡啶(摩尔比1∶2.4)的偶联反应主要生成单吡唑基取代的2-溴-6-吡唑基吡啶. 在无Pd(OAc)2/PPh3存在的情况下,则主要生成双吡唑基取代的2,6-二吡唑基吡啶. Pd(OAc)2与2-溴-6-吡唑基吡啶反应生成的配合物中间体可能抑制了双吡唑基取代产物的生成,从而影响产物分布.     

吡啶高三蝶烯的合成

2-溴-4-甲基吡啶（1）经氯代和碘代反应合成了2-溴-4-碘甲基吡啶（3）,3和蒽酮（4）反应生成10,10-二（2-溴-4-吡啶甲基）-9（10H）蒽酮（5）,5在3 MPa下与NaOCH3反应得到10,10-二（2-甲氧基-4-吡啶甲基）-9（10H）蒽酮（6）,6经硼氢化钠还原得到蒽醇（7）,7在对甲苯磺酸催化...     

2,6-二溴-4-氨基吡啶的合成

从时间分辨荧光免疫分析双功能螯合剂合成需要出发,设计了2,6-二溴-4-氨基吡啶的合成路线.以2,6-二溴吡啶为起始原料,经过氧化、硝化和还原三步合成了该化合物,通过红外光谱、元素分析和熔点测定对其进行了表征.证明了该结构和合成方法的可靠性,并分别探讨了各步产物合成反应条件的影响,具有一定的参考价值.     

2-[(9-苯基)-9H-3-咔唑基]-5-[(9-对甲苯基)-9H-3-咔唑基]吡啶的合成及其光谱性能

以咔唑和2,5-二溴吡啶为初始原料,经Ullmann反应、NBS亲电取代反应和Suzuki偶联等反应,合成了一种新型的磷光配体2-[(9-苯基)-9H-3-咔唑基]-5-[(9-对甲苯基)-9H-3-咔唑基]吡啶(5),其结构经1HNMR,ESI-MS及元素分析表征。研究了5在二氯甲烷中的荧光光谱和紫外吸收光谱。     

钯催化溴代水杨醛与吡啶硼酸的Suzuki交叉偶联反应

通过研究不同种类钯催化剂[Pd(dppf)2Cl2,Pd(OAc)2,Pd(PPh3)4]、碱(Na2CO3,Na HCO3,K2CO3,K3PO4,Cs2CO3,Cs F)、溶剂(DME/H2O,DMF/H2O,Dioxane/H2O)及温度(70,80,100℃)对5-溴-3-叔丁基水杨醛与吡啶-4-硼酸制备5-(4-吡啶)-3-叔丁基水杨醛化合物的Suzuki偶联反应的影响,开发出一种高效催化吸或供电子基取代的芳基硼酸与吸电子基取代的溴代芳烃的偶联反应的方法,该反应在Pd(PPh3)4,K2CO3,Dioxane/H2O(V∶V=4∶1)、80℃的条件下产率达到97%,且具有分离简单、重现性好的特征;但对供电子基取代的溴代芳烃参与的反应催化效果一般.     

Stereoselective total synthesis of muconin

An antitumor acetogenin, muconin, was synthesized through a coupling reaction of a THF-THP segment and a terminal butenolide. The key reactions include successive ether-ring formation reaction under acidic and basic conditions or one-pot double cyclization promoted by TBAF and stereoselective reduction of acyclic ketones adjacent to the 2,6-cis THP with Zn(BH₄)₂.     

仓库害虫集合信息素的合成锈赤扁谷盗和长角扁谷盗

本文报道通过不保护羟基的10-癸炔醇-1, 在LiNH2作用下直接与W-溴代羧酸酯反应引入羟酸基团, 从而缩补了反应步骤并提高了收率。十一碳烯内酯和十三碳烯内酯的心率为14.4%和11%, 立体选择性Z>98%。     

Novel chiral dendritic diphosphine ligands for Rh(I)-catalyzed asymmetric hydrogenation: remarkable structural effects on catalytic properties

[reaction: see text] A series of dendritic ligands with a chiral diphosphine located at the focal point have been synthesized through coupling of pyrphos 2 with Fréchet-type polyether dendron 3. The relationship between the primary structure of the dendrimer and its catalytic properties was established in the Rh-catalyzed asymmetric hydrogenation of alpha-acetamido cinnamic acid 4. A remarkable structural effect on catalytic activity was observed.     

Syntheses of Amino Group‐Substituted N‐Confused Porphyrins

Tetraphenyl N‐confused porphyrins (NCTPP) bearing amino substituents were synthesized for the purpose of functionalization toward water‐soluble and biocompatible molecules. The Pd‐catalyzed coupling reaction of 4‐ethynylaniline with the 2‐bromo NCTPP Ag(III) complex yields Pd(II) and Ag(III) coupling products ( 4a and 4b ), at 39% and 55%, respectively. The identities of these products were confirmed by the differences in the isotope patterns of their molecular ion peaks as well as other spectroscopic data. The Ag(III) coupling product, 4b , was demetallated to form the final product, 5 , with a yield of 85%. The meso‐tetrakis(4‐nitrophenyl) N‐confused porphyrin, 6 , was synthesized through a methanesulfonic acid catalyzed condensation of pyrrole with the 4‐nitrobenzaldehyde with a yield of 6.8%. Reduction of the compound to meso tetrakis(4‐aminophenyl) N‐confused porphyrin, 7 , was achieved with a yield of 90%.     

Synthesis of (‐)‐herbertenediol and (aR,aS)‐mastigophorenes A via asymmetric intramolecular heck coupling reaction

Total enantioselective synthesis of the natural (‐)‐Herbertenediol (1) was accomplished in eleven steps with an overall yield of 15% starting from the 2‐methoxy‐4‐methyl‐phenol. The total synthesis features asymmetric intramolecular Heck reaction and Wolff‐Kishner‐Huang reduction. (aR, aS)‐Mastigophorenes A was also synthesized through the oxidative coupling reaction.     

新试剂2-(2-氰基-4-硝基-6-溴苯偶氮)-6-异丙基苯酚的合成及金属离子显色反应

本文以２－氰基－４－硝基－６－溴苯胺为原料，经重氮化后与邻异丙基苯酚偶联，合成２－（２－氰基－４－硝基－６－溴苯偶氮）－６－异丙基苯酚，用乙醇重结晶精制。用元素分析，波谱等鉴定其结构，并测定其离解常数，研究该试剂的一般性质。发现其与Ｃｕ２＋、Ｎｉ２＋、Ｃｏ２＋等的显色反应在吐温８０表面活性剂存在下有较高的灵敏度。     

Assembly of a heterobinuclear 2-D network: a rare example of endo- and exocyclic coordination of Pd(II)/Ag(I) in a single macrocycle

The S3O2 macrocycle L1 was synthesized by a dithiol-dihalide coupling reaction under high-dilution conditions. The reaction of L1 with K2PdCl4 afforded an exocoordinated complex 1, [cis-Cl2Pd(L1)], which can then be manipulated to provide a heterobinuclear complex 3, {[Pd(L1)Ag(NO3)(2.5)](NO3)(0.5)}n, utilizing endocyclic Pd(II) and exocyclic Ag(I) in a single macrocycle through a successive reaction with AgNO3. The network of 3 contains a unique honeycomb-like 2-D sheet made up of the repeating unit [Ag6(NO3)6].     

MnCl_2催化交叉偶联合成沙坦联苯的工艺改进

以对氯甲苯为原料,THF为溶剂,经 Grinard反应制得对甲苯基氯化镁格氏试剂,在MnCl2催化下格氏试剂与邻氯苯腈发生交叉偶联反应制得沙坦联苯,总收率80%,纯度大于99%.     

迭代Suzuki偶联反应合成全氟环丁基芳基醚齐聚物的研究

对迭代Suzuki偶联反应合成全氟环丁基芳基醚齐聚物的方法进行了研究, 并合成了全氟环丁基芳基醚齐聚物. 首先从对溴苯酚出发, 合成了含有一个全氟环丁基芳基醚结构单元的中间体3. 芳基硼酸与中间体3进行Suzuki偶联反应, 得到了含有一个全氟环丁基芳基醚结构单元的硼酸. 重复与中间体3进行Suzuki偶联反应, 从而合成了全氟环丁基芳基醚二聚体和三聚体. 最后通过热环化二聚反应合成了全氟环丁基芳基醚三聚体、五聚体和七聚体.     

Efficient synthesis of 3-benzoyl Benzo[b]thiophenes and raloxifene via Mercury(II)-Catalyzed cyclization of 2-alkynylphenyl alkyl sulfoxides

The unique selective estrogen receptor modulator, Raloxifene (1), and antitubulin agent 2 were synthesized through the key intermediate, 4-methoxybenzyl 2-bromo-4-methoxyphenyl sulfoxide (6), respectively. It was found that compared with the o-sulfanyl aryl bromides, the sulfinyl group at ortho position accelerated the Sonogashira coupling reaction of aryl bromides. Thus, compound 6 was coupled with 3,4,5-trimethoxyphenyl acetylene, followed by mercury-catalyzed cyclization reaction afford compound 2 in 79% overall yield. Raloxifene (1) was prepared from compound 6 in four steps and 33% overall yield via coupling reaction with 1-trimethylsily-2-(4-tert-butyldimethylsiloxy)phenylethyne, mercury-catalyzed cyclization reaction, alkylation and demethylation.