Synthesis and Structure Determination of (2S, 2′S)-3-Phenyl-2-(pyrrolidin-2′-yl)- propionic Acid

Abstract

Aβ²,β³-homoproline derivative, (2S, 2′S)-3-phenyl-2-(pyrrolidin-2′-yl)propionic acid, was synthesized starting from l-proline. After preparation of the (4S, 4aS)-4-benzyl-4a,5,6,7-tetrahydro-pyrrolo-[1,2-c]pyrimidine-1,3-dione under a mild condition, the absolute configuration of target compound was assigned using 2D H-H COSY and H-H NOESY technologies.     

棒丝氨酸的全合成研究 Ⅰ.从D-葡萄糖合成3-[(3′R,5′S)-7′-氧代-1′-氮杂-4′-氧杂双环[3.2.0]-庚-3′-基]-3-O-苄基-(2S,3S)-丝氨酸及其(3′R,5′R)-差向异构体

以D-葡萄糖为原料经侧链氨基酸合成,与β-内酰胺缩合,嗯唑烷环合和除保护基等反应合成了棒丝氨酸的O-苄基衍生物,3-[(3′R,5′S)-7′-氧代-1-氮杂-4-氧杂双环[3.2.0]-庚-3′-基]-3-O-苄基-(2S,3S)-丝氨酸(17)及其(3′R,5′R)差向异构体(18)。     

Synthesis of 2′-5′,3′-5′ linked triadenylates

2′-5′,3′-5′ Linked triadenylates have been synthesized by direct bisadenylylation of adenosine 2′ and 3′ hydroxyls with an adenosine 5′-phosphorochloridite followed by oxidation.     

Synthesis and biological activity of the (−)-(2R,3S,4S)-3-azido-4-methoxy-2-(1′S-methoxy-2′-azido)ethyl-thiolane

A stereospecific ring contraction reaction, promoted by NaN₃, was detected starting from a thiepane derivative obtained from d-sorbitol, an inexpensive alcohol sugar. The major polyfunctionalized thiolane derivative obtained was investigated as a potential glycosidase inhibitor.     

Synthesis of (1′S*,2R*,3R*)- and (1′S*,2R*,3S*)-N-arylsulfonyl-2-(1′-halogenethyl)-3-methylindolines and their selective toxicity against SH-SY5Y cell line

N-tosyl-2- and N-tosyl-4-halogen-substituted derivatives of 2-(1-methylbut-2-en-1-yl)aniline were synthesized and their molecular iodine-mediated cyclization was investigated. The cyclization upon interaction of N-tosyl-6-methyl-2-(1-methylbut-2-en-1-yl)aniline with molecular iodine in methyl tert-butyl ether or acetonitrile was studied, as well as the interaction of this sulfonamide with N-bromosucinimide in dichloromethane. Synthesized (2R*,3R*)- and (2R*,3S*)-N-arylsulfonyl-2-(1-halogenoethyl)-3-methylindoline derivatives showed cytotoxic activity against HEK293 cells, SH-SY5Y, Jurkat, and HepG2 cell lines. The compounds (2R*,3S*)-N-arylsulfonyl-7-bromo-2-(1-halogenoethyl)-3-methylindoline cis- 4a , stereoisomeric (2R*,3R*)-trans- 4h and (2R*,3S*)-N-tosyl-7-chloro-2-(1-halogenoethyl)-3-methylindoline cis- 4h demonstrated selective toxicity against SH-SY5Y cell line (IC₅₀ ≈ 3 ÷ 5 μM), and did not affect HEK293, Jurkat, and HepG2 cells.     

2′-脱氧-2′-氟-2′-尿嘧啶-3′,4′-O-异亚丙基-L-阿拉伯糖甲苷的合成

目前,氟代糖和氟代糖苷在抗肿瘤和抗病毒的研究方面已引起人们的广泛兴趣,由于     

5，8，5′，8′-二甲氧基-3，3′-二亚甲基-2，2′-双喹啉的合成

2-氨基-3,6-二甲氧基苯甲醛与1,2-环己二酮发生Fried lander缩合反应合成了新化合物5,8,5,′8′-二甲氧基-3,3′-二亚甲基-2,2′-双喹啉,其结构经UV,1H NMR,IR和MS表征。     

2-[-1′-(4′-甲基-3′-戊烯基)]-2-甲基苯并呋喃的合成研究

许多天然产物(如黄酮、香豆素、苯丙素)分子结构中含有2-[-1′-(4′-甲基-3′-戊烯基)]-2-甲基苯并呋喃(1a)和1b的结构单元,如,具有抗肿瘤生物活性的Sanggenol L 4和Kuwanol 5[1].因此寻找1a和1b便利有效的合成方法具有重要的合成价值.我们采用2,4,6-三羟基苯乙酮(2a)[或2,4-二羟基苯乙酮(2b)]为原料,与柠檬醛3在有机碱(吡啶、三乙胺、N,N-二乙基苯胺)的作用下,一步反应以较好的收率40%～70%分别获得1a和1b结构单元.     

2-(2′-羟基-3′-甲氧基苯基)-5,6-二硝基苯并咪唑的阴离子识别

设计并合成了2-(2′-羟基-3′-甲氧基苯基)-5,6-二硝基苯并咪唑化合物(1),通过X射线单晶衍射研究了该化合物的固态结构.利用紫外-可见光谱技术研究了其对阴离子的识别,发现化合物1能够在DMSO中对AcO-,H2PO4-,OH-的3种离子进行有效识别,同时溶液由原来的黄色变成红色,实现裸眼检测.     

Synthesis of 3-(3′-Acetyl-5′-aroyl-1′,3′,4′-oxadiazolyl-2′)-chromones

A general method has been proposed for synthesizing 3-(3-acetyl-5-aroyl-1,3,4-oxadiazolyl-2)-chromones that has been based on conversion of 3-formylchromones to acylhydrazones and of theacylhydrazones into the heterocyclic chromones.     

3-(3′-芳基-5′-硫酮-1′,2′,4′-三唑-4′-基)-氨甲酰基色酮类化合物的合成

报道 3 甲酰基色酮经Jones试剂氧化后得到 3 羧基色酮 ,再与 3 芳基 4 氨基 5 硫酮 1,2 ,4 三唑在POCl3 作用下 ,得到一系列 3 (3′ 芳基 5′ 硫酮 1′ ,2′,4′ 三唑 4′ 基 ) 氨甲酰基色酮类化合物 .所有化合物的结构均经IR ,LC MS ,1HNMR ,元素分析确证     

Microwave promoted one-pot synthesis of 3-(2′-amino-3′-cyano-4′-arylpyrid-6′-yl)coumarins

A facile procedure for the synthesis of 3-(2′-amino-3′-cyano-4′-arylpyrid-6′-yl)coumarins are being reported starting from 3- acetylcoumarin,aromatic aldehydes and malononitrile.The reactions were carded out on microwave irradiation in good yield with short time and easy work-up.The structures of all the compounds have been confirmed on the basis of their analytical,IR,~1H NMR, and mass spectral data.     

Darstellung von 2′,3′-Dideoxy-2′-hydroxymethyl-nucleosiden

Zusammenfassung Die Synthese von geschützten 2,3-Dideoxy-2-hydroxymethyl-nucleosiden wird beschrieben. Die durch ein Mehrstufenverfahren aus Isopropylidenglycerol erhaltenen Nucleoside können als Bausteine zur Darstellung von Oligonucleotiden verwendet werden, deren 2- und 5-Positionen über eine Etherbrücke verbunden sind.

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Synthesis of 2,3-dideoxy-2-hydroxymethyl nucleosides

Summary The synthesis of protected 2,3-dideoxy-2-hydroxymethyl nucleosides is presented. The nucleosides, obtained in a multi-step procedure starting from isopropylideneglycerol, may be used as building blocks for the synthesis of 2,5-ether linked oligonucleotides.

     

2′-Fluoro-3-deazaaristeromycin

The carbocyclic nucleoside 3-deazaaristeromycin has shown biological promise but a library of its derivatives upon which to expand this property is lacking. To address this situation, the synthesis of the two diastereomers of 2′-fluoro-3-deazaaristeromycin is described in a multistep convergent process that calls upon d-ribose for construction of the cyclopentyl fluoro units.     

Synthesis and structural characterization of camphanates of (−)-(2S3S,3S) and (+)-(2S,3R)-4-Phenyl-3-bromo-2-butanol diastereoisomers

The X-ray crystal structures of (–)-syn-4-phenyl-3-bromo-2-butyl camphanate (I) and (+-anti-4-phenyl-3-bromo-2-butyl camphanate (II) have been determined. Thesyn diastereoisomer of bromohydrin has the (2S,3S) absolute configuration whereas theanti diastereoisomer has the (2S,3R) absolute configuration. The crystallized derivatives I and II have been obtained by the reaction of each stereoisomer of bromohydrin, synthesized by reduction with baker's yeast, with (1S)-camphanic chloride. Crystal data: (I) C₂₀H₂₅BrO₄:M _w: 409.32; orthorhombic,P2₁2₁2₁;a=11.245(3),b=12.086(1),c=14.512(4) å; Z=4; finalR=0.053 for 1819 observed reflections. (II) C₂₀H₂₅BrO₄;M _w=409.32; monoclinic, P2₁;a=11.352(1),b=6.378(1),c=14.255(2) å,=110.38(1);Z=2; finalR=0.045 for 1672 observed reflections.     

2′-羟基-1′,3′-苯撑二亚甲基冠醚的合成

2,6-二羟甲基-4-氯苯甲醚(3)和2,6-二羟甲基-4-苯基苯甲醇(4)与三缩四乙二醇和四缩五乙二醇的二对甲苯磺酸酯在含有叔丁醇钾的无水四氢呋喃中反应生成甲氧基冠醚5—7。后者与过量无水碘化锂在无水吡啶中廻流有选择性地除去甲基而不影响大环苄醚基的破裂生成三种2’-羟基-1’,3’-亚苯基二甲基冠醚8—10,产率为85—89％。     

由2′,4′-二氢-6′-甲氧基-3′,5′-二甲基查耳酮合成新黄酮

在DMSO/I2的氧化作用下,由2′,4′-二氢-6′-甲氧基-3′,5′-二甲基查耳酮可合成一种全新结构的黄酮:7-羟基-5-甲氧基-6,8-二甲基黄酮(产率91%),而在HCl/MeOH作用下则得到了两种黄烷酮:7-羟基-5-甲氧基-6,8-二甲基黄烷酮(产率70%)和5,7-二羟基-6,8-二甲基黄烷酮(产率20%)。     

2, 2′-联吡啶-3, 3′二羧酸铱配合物的合成、晶体结构和发光性质研究

利用环金属配体2-苯基吡啶(ppy)和辅助配体2,2'-联吡啶-3,3’-二羧酸(H2dcbpy)合成了一个铱配合物[Ir(ppy)2(Hdcbpy)],并且测定了其晶体结构。通过对配合物的紫外可见吸收光谱和发光光谱的研究表明,其常温发射位于620nm处,初步推测该磷光发射可能来自由金属到环金属配体和辅助配体的电荷转移(MLCT)跃迁。     

Synthesis of β-L-2′,3′-Dideoxy-2′-fluoro-3′-hydroxymethylarabinofuranosyl Pyrimidine Nucleosides

β-2′,3′-Dideoxy-2′-fluoro-3′-hydroxymethylarabinofuranosylthymine 10 and cytosine 12 were synthesized from L-xylose and were found to be inactive against HIV-1 in acutely infected lymphocytes.