光学纯Communesin F中间体的合成

以communesin F消旋体的全合成过程中的醛中间体为原料,在光学纯叔丁基亚磺酰胺的手性诱导下,通过加成和还原反应制得摩尔比为1:1的非对应异构体3a和3b;脱去3a的叔丁基亚磺酰基制得光学纯4; 4的氨基用Boc保护合成了光学纯Communesin F的重要中间体5.3～5的结构经1H NMR表征.     

光学纯环状硝酮的氧化合成

光学纯的环状硝酮具有重要的实用价值,广泛应用于天然多羟基的吡咯烷、哌啶、吡咯啉士啶以及吲哚啉士啶等生物碱的合成,因而这类硝酮化合物的合成及其在天然产物合成方面的应用越来越引起人们的重视。环状的羟胺、仲胺、亚胺、吡咯啉、异噁唑烷氧等化合物的氧化是这类硝酮化合物最方便的合成方法,本文就这类光学纯环状硝酮的氧化合成作一简要评述。     

化学-酶法合成多肽的研究进展

多肽是涉及生物体内各种细胞功能的生物活性物质, 它是分子结构介于氨基酸和蛋白质之间的一类化合物, 由多种氨基酸按照一定的排列顺序通过肽键结合而成. 多肽类药物具有安全、副作用小、用量小(以mg计)、功能多样、特异性强等特点, 在细胞生理和代谢功能的调节上及抗肿瘤等方面具有重要作用[1].     

(±)-亮氨酸的合成

以氨基丙二酸二乙酯盐酸盐(2)为原料通过一条全新路线合成了外消旋亮氨酸盐酸盐(1)。2的氨基经Boc保护制得Boc-氨基丙二酸二乙酯(3);3与甲代烯丙基氯发生取代反应制得Boc-氨基-(2-甲基-2-丙烯基)丙二酸二乙酯(4);4经Pd/C催化加氢制得Boc-氨基-(2-异丁基)丙二酸二乙酯(5);5在浓盐酸中回流反应,一步完成脱保护、脱羧、水解过程合成1。总收率55%,其结构经1H NMR和MS确证。     

苯丙氨酸光学异构体的酶法拆分

氨基酰化酶;苯丙氨酸光学异构体的酶法拆分     

环亮氨酸的合成

以甘氨酸为起始原料,经酯化、酰胺化、脱水、成环及水解5步反应后,过阳离子交换柱合成了环亮氨酸,总收率52%,其结构经1H NMR和IR确证.     

可生物降解高分子的酶法合成和改性

介绍了新型功能高分子材料－可生物降解高分子材料的研究概况，并重点评述了这一领域研究的新分支－酶法合成可生物降解高分子材料的新进展。     

酶法合成头孢丙烯工艺研究

采用酶催化法,以7-氨基-3-[(Z)-烯丙-1-基]-3-头孢环-4-羧酸(7-APCA)为母核,D-对羟苯甘氨酸甲酯(D-HPGME)为酰基供体,水作溶剂,在固定化青霉素G酰化酶的催化作用下合成头孢丙烯。本研究中催化酶的载体采用氨基和环氧载体,筛选合适的酶活,考察反应pH、温度、投酶量、投料比、底物浓度等多个因素对酶法合成头孢丙烯的影响。通过对酶法合成头孢丙烯的工艺条件的优化,为头孢丙烯绿色生产技术的推行打下基础。     

光学活性环氧化物的酶催化合成

光学活性环氧化物的酶催化合成①夏仕文尉迟力沈润南李树本②（中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室，兰州７３００００）关键词光学活性环氧化物酶催化不对称合成动力学拆分１前言光学活性环氧化物含有两个手性碳，通过选择性开环和官能团转换...     

1-氟代糖在化学-酶法合成糖类中的应用

化学-酶法合成糖类具有立体选择性和区域选择性, 逐渐成为糖类合成的主流. 1-氟代糖作为糖基供体应用于化学-酶法合成反应, 显示出越来越重要的作用, 综述了1-氟代糖在糖基转移酶和糖苷酶催化的糖类合成中的应用.     

异戊醛胺羰合成N—乙酰基亮氨酸的催化反应研究

以 Pd Cl2 /PPh3/Na Br组成的催化剂体系催化异戊醛胺羰化反应 ,通过对配体浓度、助催化剂、反应温度、压力等的考察 ,选择出优化的反应条件 .对助催化剂碱金属溴化物中阳离子对催化活性的影响研究表明 ,碱金属阳离子对反应的促进作用顺序为 L i+ >Na+ >NH4+ >K+ .在少量硫酸存在、 90℃、 5 .0 MPa一氧化碳压力下 ,N-乙酰基亮氨酸的收率可达 76 .9%     

Synthesis of All Enantiomerically Pure Diastereomers of Aprepitant

Syntheses of all eight enantiomerically pure diastereomers of aprepitant and assignment of absolute configuration at newly generated stereocenters by NMR and x-ray crystallographic analysis were achieved.     

Stereoselective Synthesis of Enantiomerically Pure Nupharamine Alkaloids from Castoreum

An animalic note : The first total synthesis of the all‐cis nupharamine 2 , an alkaloid from beaver castoreum, is based on the stereoselective domino Mannich–Michael reaction of N‐galactosylfurylaldimine to give 1 (Piv=pivaloyl), subsequent conjugate cuprate addition, and stereoselective protonation of the enolate. These reactions are all controlled by the carbohydrate. Protonation of the enolate after cleavage of the auxiliary leads to epimer 3 .

     

First Atroposelective Total Synthesis of Enantiomerically Pure Ancistrocladidine and Ancistrotectorine

The first regio‐ and stereoselective total synthesis of the axially chiral 7,3′‐coupled naphthylisoquinoline alkaloids ancistrocladidine ( 1 ) and ancistrotectorine ( 2 ) has been described. Both possess a 7,3′‐coupled axis, which before now, was difficult to attain synthetically. Moreover, target 2 has a sensitive relative cis‐array of the two methyl groups at C1 and C3 in the tetrahydroisoquinoline part. The key step in the chosen strategy was the construction of the biaryl axis in accordance with the “lactone method”: the two molecular halves, which were activated in an “inverse‐halogenated” form, were prefixed by an ester bridge, followed by intramolecular coupling, and atroposelective cleavage of the lactone auxiliary bridge delivered the desired biaryl scaffold.     

Chemoenzymatic total synthesis of cryptocaryalactone natural products

A new chemoenzymatic route for the preparation of cryptocaryalactones natural products using a kinetic resolution process as the key step is described. Novozyme-435 catalyzed hydrolysis of the prochiral (±)-monoester 7 afforded the precursors of cryptocaryalactones with high enantiomeric excess and excellent yields. The compounds (4S,6S)-7 and (4R,6R)-7 were converted to (+)-(6R,2′S)-cryptocaryalactone (1) and (?)-(6S,2′R)-cryptocaryalactone (2), respectively by employing Wittig-olefination, lactonization and acylation reactions.     

N-硬脂酰基亮氨酸的合成

采用酰氯化反应与缩合反应两步法合成N -硬脂酰基亮氨酸。以硬脂酸和亚硫酰氯为原料 ,n(硬脂酸 )∶n(亚硫酰氯 ) =1∶1 .5 ,在 80℃下冷凝回流 6h酰氯化反应合成硬脂酰氯 ,硬脂酰氯经减压蒸馏收集 1 70～2 0 0℃的馏分得到。硬脂酰氯收率为 65 %。硬脂酰氯再与亮氨酸的氢氧化钠溶液在冰水浴中进行Schotten -Baumann缩合反应制得N -硬脂酰基亮氨酸。缩合反应最佳工艺条件是反应溶液pH值控制为 9.0。反应后滴加1mol/L盐酸至pH =5 .0～ 6.0 ,加入正己烷使N -硬脂酰基亮氨酸处于水层中 ,分离并蒸干水层溶液得含NaCl的混合物。用无水乙醇萃取混合物 ,萃取液蒸干得产物。N -硬脂酰基亮氨酸收率为 75 %     

Synthesis of Enantiomerically Pure 2-Isoxacephems

Summary. (R,6R,7R)-7-(1-Acetoxyethyl)-3-methyl-2-isoxacephem-4-carboxylic acid and its enantiomer have been prepared. The ring systems were formed from the corresponding enantiomerically pure N-unsubstituted -lactams. The reduction of methyl [(R,2S,3R)-3-(1-acetoxyethyl)-1-(4-methoxyphenyl)-4-oxoazetidine-2-carboxylate] has been solved via a hemi-acetal. The structure and the configuration of a new stereogenic center in this intermediate was predicted by using 2D NMR technique and unambiguously proven by x-ray.     

Synthesis of Enantiomerically Pure 2-Isoxacephems

(R,6R,7R)-7-(1-Acetoxyethyl)-3-methyl-2-isoxacephem-4-carboxylic acid and its enantiomer have been prepared. The ring systems were formed from the corresponding enantiomerically pure N-unsubstituted -lactams. The reduction of methyl [(R,2S,3R)-3-(1-acetoxyethyl)-1-(4-methoxyphenyl)-4-oxoazetidine-2-carboxylate] has been solved via a hemi-acetal. The structure and the configuration of a new stereogenic center in this intermediate was predicted by using 2D NMR technique and unambiguously proven by x-ray.     

Enantiomerically Pure Tribenzotriquinacenes through Stereoselective Synthesis

Inherently chiral acetophenones and benzaldehydes bearing the large, bowl‐shaped framework of tribenzotriquinacene (TBTQ) were synthesized in enantiomerically pure form employing enzyme catalysis. Five‐step sequences involving lipase CAL‐B lead to the (M)‐enantiomers, (+)‐2‐acetyl‐TBTQ (M)‐ 5 and (+)‐2‐formyl‐TBTQ (M)‐ 6 , whereas use of lipase PS leads to the (P)‐enantiomers, (?)‐2‐acetyl‐TBTQ (P)‐ 5 and (?)‐2‐formyl‐TBTQ (P)‐ 6 , with at least 99 % ee in each case. The absolute configuration of these rigid 3D building blocks was determined by X‐ray diffraction analysis of the ketones 5 and by comparison of their chiroptical properties with those of the aldehydes 6 .     

A Chemoenzymatic Approach to Enantiomerically Pure Amines Using Dynamic Kinetic Resolution: Application to the Synthesis of Norsertraline

Dynamic transformation : A racemization catalyst and the enzyme Candida antarctica lipase B (CALB) were combined in a one‐pot dynamic kinetic resolution (DKR) of primary amines, which were transformed to their corresponding amides in up to 95 % yield and >99 % ee. This chemoenzymatic DKR was also applied to the synthesis of norsertraline (see scheme).