用Heck反应合成1-羟基-4-(3-吡啶基)丁-2-酮

在Heck反应条件下,以Ph3P为催化剂配体,由3-卤代吡啶和3-丁烯-1,2-二醇进行偶合可以得到1-羟基-4-(3-吡啶基)丁-2-酮,具有原料易得、合成方法简单的优点.     

R和S-1-(3′-溴-4′-甲氧基)苄基-2-甲基-6-甲氧基-7-羟基-1,2,3,4-四氢异喹啉的合成

单醚链和双醚链的节基四氢异喹啉在生物碱中较为长见。一般合成这类四氢异喹啉,是合成在一定位置上有溴的四氢异喹啉,然后与另一含羟基的四氢异喹啉通过Ullmann反应     

Synthesis and Crystal Structure of (2S,2'S,4'R)-2-(1-Hydroxy-1-ethylpropyl)-1-[(1'-p-tosyl-4'-hydroxypyrrolidin-2'-yl)methyl]pyrrolidine

1 INTRODUCTION In recent years, chiral β-amino alcohols have attracted much attention due to their special bio- logical functions and catalytic activities. Chiral β- amino alcohol moieties are usually found not only in natural products (e.g., cinchona alkaloids, ephe- drine, toxal, etc.) with special biological activities[1, 2], but also critical structural segments of some syn- thesized biologically active compounds, such as adrenergic agonists or antagolist[3, 4] and inhibitors for HI…     

1-(2-Iodophenyl)-1H-tetrazole as a ligand for Pd(II) catalyzed Heck reaction

1-(2-Iodophenyl)-1H-tetrazole 2 was synthesized by the reaction of 2-iodoaniline, sodium azide and triethyl orthoformate in acetic acid. The newly synthesized ligand 2 was successfully used in Heck reaction to give the cross-coupled products in excellent yields.     

Reagent control of stereochemistry in allylic additions to chiral aldehydes with CpMo(NO)(X)(2-methallyl) complexes of high enantiomeric purity

Reactions of (R)- and (S)-CpMo(NO)(η³-methallyl)X(X=camphorsulfonate, Cl, Br, I) with chiral α-substituted aldehydes yield homoallylic alcohols with high diastereoselectivity. Reactions of (R)- and (S)-CpMo(NO)(η³- methallyl)L ^S[L^S = (IS)-(+)-10-camphorsulfonate] with D -glyceraldehyde acetonide yield the corresponding homoallylic alcohols in >98% diastereomeric excess. Reactions with racemic 2-phenyl-propionaldehyde and nonracemic 3-benzyloxy-2-methylpropanol are also considered and show that there is very high reagent control of stereo-chemistry in additions to the carbonyl group.     

手性液晶掺杂剂（S）—4‘—辛氧基—4—（2—酰氧基—丙氧基）联苯的合成

手性液晶掺杂剂（Ｓ）┐４┐辛氧基┐４┐（２┐酰氧基┐丙氧基）联苯的合成马汝建李培荣国斌＊（华东理工大学化学系上海２００２３７）关键词铁电液晶材料，手性液晶掺杂剂，合成，手征性１９９７－０２－０３收稿，１９９７－０８－０７修回铁电液晶显示器所用的材料...     

First Enantioselective Synthesis of (2R,3R)-and(2S,3S)-2-(4-hydroxyphenyl)-3-hydroxymethyl-1,4-benzodioxan-6-carbaldehyde

Numerous lignans containing 1,4-benzodioxane nucleus represent a class of natural products with cytotoxic and hepatoprotective activities1,2. Recently we have reported the racemic total synthesis of sinaiticin, a flavonolignan of the 1,4-benzodioxane type which was isolated from sinaiticum leaves found in sinai region of Egypt, using 2-(4-hydroxyphenyl)-3-hydroxymethyl-1,4-benzodioxan-6-carbaldehyde as the key interme-diate3,4. This species exhibits significant inhibitory activity against the …     

Catalyst- and steric-controlled alkenylation via chemoselective C-H activation and C-Br activation in Heck reaction of methyl 1-(2-bromoaryl)-3-(2-furyl/thienyl)-5-oxopyrrolidine-2-carboxylates and diethyl 1-(2-bromoaryl)-3-(2-furyl/thienyl)-5-oxopyrrolidine-2,2-dicarboxylate derivatives

Pd(II)-catalyzed alkenylation of methyl 1-(2-bromoaryl)-3-(2-furyl/thienyl)-5-oxopyrrolidine-2-carboxylate derivatives 1(a-d) resulted in the formation of 3(a-d) exclusively via C-H activation in the heteroaryl moiety. Similar observations were observed for the corresponding diester analogues 4(a-d) to form 5(a-d). Normal Heck reaction, however, was observed in the case of 1(a-f) to furnish 2(a-f) when the reaction was carried out with Pd(0) catalyst generated in situ. Pd(0)-catalyzed vinylation of 4(a-f) via C-Br oxidation, however, failed due to steric reason.     

Chemistry of 3-(1H-Indol-3-yl)-3-oxopropanenitrile

This review highlighted the methods used for the synthesis of different heterocyclic compounds derived from 3-(1H-indol-3-yl)-3-oxopropanenitrile. The reactivity and their synthetic importance were investigated. In this context, recent progress in the synthesis and use of 3-(1H-indol-3-yl)-3-oxopropanenitrile as precursors for heterocyclic compounds is reviewed.     

Ethyl 3,3-diamino-2-(2-p-tolylpyrimidin-4-yl)acrylate,a new representative of hetarylketene aminals

A new representative of hetarylketene aminals, ethyl 3,3-diamino-2-(2-p-tolylpyrimidin-4-yl)acrylate, was synthesized by the reaction ofp-toluamidine with the condensation product of dimethylformamide dimethyl acetal and the difluoroboron chelate of acetyl(ethoxycarbonyl)ketene (N-benzoyl)aminal. This synthesis is an example of pyrimidine ring assembly using the methodology based on transformations of chelate complexes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1638–1640, September, 1994.This research was partially supported by the International Science Foundation (Grant No. M5QOOO).     

An efficient chiral synthesis of (R)-N-[3-acetyl-4-(2-hydroxy-3-isopropylamino-propoxy)phenyl]-butanamide with high enantioselectivity

R-Enantiomer of the β-receptor antagonist N-[3-acetyl-4-(2-hydroxy-3-isopropylamino-propoxy)phenyl] butanamide with high enantioselectivity was synthesized from cheap starting materials and enantiopure chiral reagent through an efficient,convenient and practical synthetic strategy.Title product was detected by 1H NMR,13C NMR,and MS,and the enatiomeric excess was determined by chiral HPLC analysis using a chiracel AD-H column.     

N-(S)-(1’-氯甲基-2’-烷基)-2-乙基-2-(4S-烷基-4,5-二氢噁唑)丁酰胺的合成

由L-氨基酸不对称合成了4种新型手性化合物(6a,6b,7a,7b),其结构经IR,~1H NMR,~(13)C NMR及MS等证实。     

(4R)-5,5-二甲基-4-苄硫甲基-2-噁唑烷酮的合成

以价廉易得的天然L-半胱氨酸为原料,经巯基保护、酯化、氨基保护、格氏反应及环化等5步反应,合成了一个新的手性助剂(4R)-5,5-二甲基-4-苄硫甲基-2-噁唑烷酮,总收率31%.产物结构经IR,~1H NMR,~(13)C NMR及MS表征.     

Syntheses of Two Chiral Clusters [η5—C5H4C（NR）CH3]—RuNiM（CO）5（μ3—S）（R=NH—C6H3—2,4—（NO2）2,M=Mo,3;M=W,4）and the Single—crystal Structure of Cluster 3

1 INTRODUCTION The synthesis of chiral clusters containing four different atoms at the vertexes of the tetrahedron has been extensively studied because the chiral cluster can induce an asymmetric catalysis potentially[1]. Until now, many tetrahedron-type chiral clusters have been reported, but only a few of the reactions about the organic group in these clusters were investi- gated[2～4]. In this paper, we described the syntheses of clusters 3 and 4, and the structure of the former. 2 …     

4-[2-(9,9-二辛基-9H-芴-2-)乙烯基]苯胺的合成及其光学性质

以2-溴芴、溴代正辛烷和对硝基苯乙烯为主要原料,通过烷基化反应、Heck反应和还原反应合成了新化合物4-[2-(9,9-二辛基-9H-芴-2-]乙烯基)苯胺(5),其结构经1H NMR和IR表征。应用UV-Vis和荧光光谱初步探讨了5的光学性质。     

An efficient chiral synthesis of (R)-N-[3-acetyl-4-(2-hydroxy-3-isopropylamino-propoxy)phenyl]-butanamide with high enantioselectivity

R-Enantiomer of the β-receptor antagonist N-[3-acetyl-4-(2-hydroxy-3-isopropylamino-propoxy)phenyl] butanamide with high enantioselectivity was synthesized from cheap starting materials and enantiopure chiral reagent through an efficient, convenient and practical synthetic strategy. Title product was detected by ¹H NMR, ¹³C NMR, and MS, and the enatiomeric excess was determined by chiral HPLC analysis using a chiracel AD-H column. Supported by the National Natural Science Foundation of China (Grant Nos. 20472090 & 10576034) and PLA General Armament Department (Grant No. 9140A28010707zk7301)     

手性邻二醇－－（2S，3R）－1，2，3－丁三醇－1－对甲苯磺酸酯的不对称合成

以（E）－2－丁烯－1－醇为原料经不对称环氧化反应合成2，3－环氧醇（1） 。该环氧醇的对甲苯磺酸酯对映选择性酸水解开环制备手性邻二醇（2）(95％ee)。