（±）—Salvinolone的全合成研究

以２－（３，４－环己基类二氧－５－异丙基）苯基乙醇（２）和３－异丙氧基－５，５－二甲基－１，３－环己烯酮（４）为原料，利用羰基α－位的烷基化反应和分子内的Ｆｒｉｅｄｅｌ－Ｃａｒｆｔｓ反应为关键步骤，经９步反应，合成了多氧芳香型三环二萜类天然产物Ｓａｌｖｉｎｏｌｏｎｅ。     

Brefeldin A全合成研究新进展

Brefeldin A(布雷菲德菌素甲)是一种天然抗生素, 最早发现于1958年, 许多种微生物中都能产生该化合物. 由于其有趣的结构和显著的抗真菌、抗病毒、抗肿瘤等生物活性, 该化合物很早就引起合成化学家们的注意. 到目前为止, 文献中有报道的全合成和表观合成已有30多种. 对近十年来的全合成及部分表观合成进行了综述, 对各路线的主要优缺点也进行了简要的分析. 一些类似物的合成也一并予以简介.     

(S)-(+)-姜黄烯的立体选择性全合成

利用不对称双羟化反应和Raney镍的原位还原,高对映选择性和高产率地实现了(S)-(+)-α-姜黄烯(1)的立体选择性合成.用MsCl保护化合物7a和7b时,发现了有趣的消除和重排反应,得到对应的二烯化合物8.     

有机反应立体选择性描述术语%ee/er、%de/dr刍议

有机反应的立体选择性和有机化合物的立体异构现象不仅在有机化学,在药物科学和生命科学等相关学科领域中也是具有极其重要意义的研究课题之一。本文介绍了表达有机反应立体选择性高低和立体异构体纯度的几个重要描述术语——对映体过量百分数(percent enantiomeric excess,简写为%ee)、非对映体过量百分数(percent diastereomeric excess,简写为%de)、对映体比例(enantiomeric ratio,简写为er)和非对映体比例(diastereomeric ratio,简写为dr)的历史由来、含义及其在学术使用中存在的争议,给大学有机化学课程相关内容的教学提出建议。     

手性药物的对映体选择性释放

手性和手性物质的重要性已不言而喻,手性药物的开发也已成为主要发展趋势,但目前仍有部分手性药物以消旋体的形式出售和使用。如何合理、有效地使用这些消旋体药物,一直是值得深入研究的课题。对映体选择性释放将手性拆分和控释两个概念结合于一体,有望为消旋体药物的使用提供新的途径。基于本课题组的研究,本文综述了近年来对映体选择性释放研究领域所取得的主要进展。为便于讨论,本文根据构成药物控释载体的手性分子或结构(手性因素),将手性药物释放体系分为有机材料(水凝胶和粒子等)、无机材料和分子印迹材料等控释体系。关于对映体选择性释放以及释放过程中的对映选择性作用的研究,可进一步提升我们对于手性、手性物质和手性作用的认识。     

对映体的气相色谱分析Ⅱ．手性芳香二级醇的分离测定

在手性毛细管柱Ｃｈｉｒａｓｉｌ－Ｌ－Ｖａｌ（玻璃柱）、ＣＹＤＥＸ－β－全甲基化β－环糊精（交联弹性石英柱）上考察了苯乙醇腈、１－苯基－１－乙醇、１－苯基－１－丙醇、１－苯基－２,２－二甲基－１－丙醇、１－（４－氯苯基）－１－乙醇芳香二级醇对映体分离的色谱行为。并测定了一系列不对称合成实际样品中对映体过量值（即ｅ．ｅ．值）。     

手性药物的毛细管电泳拆分

以氧氟沙星、扑尔敏、特布它林和普萘洛尔为手性药物,分别采用羟丙基-β环糊精(HP--βCD)、羟丙基-β-环糊精结合羧甲基-β-环糊精(HP--βCD/CM--βCD)作手性拆分试剂,考察环糊精浓度和pH对手性选择性的影响。结果发现环糊精提供手性相互作用,而pH强烈地影响这种相互作用。以HP--βCD/CM-β-CD组成的双环糊精系统能更好地优化手性选择性,而通过调节pH可以获得需要的分离选择性、迁移次序。     

手性配体DDPPI-Pd(Ⅱ)催化α-烯烃不对称氢酯基化反应的研究

考察了手性双膦配体DDPPI在钯催化1-辛烯及官能化端烯的不对称氢酯基化反应中的手性诱导作用，最高得到了45．2％的ee值．其中在1-辛烯的不对称氢酯基化反应中，考察了不同的膦-钯比、反应温度、压力、不同的溶剂、不同的钯催化剂前体以及助催化剂对反应的影响．其中膦，钯比在2～4的范围内，催化反应获得了较高的光学产率；以丙酮作溶剂，得到较好的催化效果．     

由D-木糖衍生的实用手性合成砌块

本文报道了以价廉易得的D-木糖为起始原料合成数种尚未见报道过的含有潜在1,3-二羟基手性及末端环氧的光学活性合成砌块的简便实用方法。     

二茂铁手性膦配体研究的一些新进展

综述了具有独特结构的二茂铁手性膦配体的合成及应用. 这类化合物在催化不对称合成反应中表现出了很高的活性.     

Total Synthesis of (-)- and (+)-Balanol(1)

Two total syntheses of the potent protein kinase C inhibitory fungal metabolite balanol are described. In the first approach, the core aminohydroxyazepane subunit was prepared in racemic form by stereospecific functionalization of N-benzyl-epsilon-caprolactam. Resolution prior to coupling to the benzophenone subunit provided access to both enantiomers of balanol. In the second approach, an efficient silicon-mediated cyclization of (2S,3R)-3-hydroxylysine followed by reduction provided the azepane subunit in enantiomerically pure form. The sterically congested benzophenone subunit was assembled from two highly substituted aromatic precursors by way of an anionic homo-Fries rearrangement.     

Syntheses of (+)- and (–)-Methyl 8-Epinonactate and (+)- and (–)-Methyl Nonactate

In four synthetic steps, (+)- and (–)-methyl 8-epinonactate ((+)- and (–)− 4 ) have been derived from (+)- and (–)-7-oxabicyclo[2.2.1]heptan-2-one ((+)- and (–)− 9 ), respectively. The (+)- and (–)-methyl nonactate ((+)- and (–)− 3 ) were obtained from (+)- and (–)− 4 , respectively, by Mitsunobu displacement reactions. Optical resolution of (±)− 9 via chromatographic separation of the corresponding N-methyl-S-alkyl-S-phenylsulfoximides 24 and 25 yielded the starting materials (+)- and (–)− 9 , respectively.     

Chiral Diselenides in the Total Synthesis of (+)-Samin

Chiral selenium compounds are applied to stoichiometric as well as to catalytic reactions in the synthesis of substituted tetrahydrofuran derivatives: The selenium compound 1 was used in catalytic amounts for a rapid access to chiral diselenide 3. The efficient stereoselective addition to alkene 5 yields product 8 with a selenium functionality as a precursor for an intramolecular radical cyclization. In this way a short total synthesis of (+)-samin (11), a naturally occurring furofuran lignan, was achieved.     

Studies Culminating in the Total Synthesis and Determination of the Absolute Configuration of (-)-Saudin

A full account of studies that culminated in the total synthesis of both antipodes and the assignment of its absolute configuration of Saudin, a hypoglycemic natural product. Two approaches are described, the first proceeding though bicyclic lactone intermediates and related second monocyclic esters. The former was obtained via asymmetric Diels-Alder cycloaddition and the latter by an asymmetric annulation protocol. Both approaches employ a Lewis acid promoted Claisen rearrangement, with the successful approach taking advantage of bidentate chelation to control the facial selectivity of the key Claisen rearrangement.     

A Convenient Synthesis of (-)-Methyl Epijasmonate

A short, enantioselective synthesis of (-)-methyl epi-jasmonate, ent-1, has been achieved starting from readily available Corey lactone aldehyde 9. The key features include the stereoselective installation of 2,3-cis-disubstituted side-chains by hydrogenation of dienoate 8 and subsequent one-carbon degradation.     

Chiral Synthesis of the Intermediate of (-)-Gibberellin A_(12)

Inthepreviouspapers,wereportedtotalsynthesesofditerpenoidsofC-2oQseriessuchas(+)-podocarpicacid(:),andcalabarbeanalkaloid(-)-physostigmine("from(S)-(-)-2-methyl-2-(2'-nitrovinyl)-5-valerolactone.Herewereportasynthesisofthekeyintermediate(l)for(-)-gibberellinA,=using(R)-(+)-2-methyl-2-(2'-nitrovinyaSachiralbuildingblock.(R)-(+)-2-methyl-2-(2'-nitrovinywassynthesizedaccordingtoliteratUremethod(3)in95%yieldand9l%ee.TheMichaeladditionofbenZylInagnesiumbromideto(R)-nitroolefm2affordedadiastereo…     

Total synthesis of (-)- and (+)-lentiginosine

Total synthesis of (-)-lentiginosine was achieved from D-mannitol using highly stereoselective reactions. Similarly, (+)-lentiginosine was synthesized from L-tartaric acid.