NEW METHODS FOR THE PREPARATION OF SULFOXIMINES

Abstract

Three methods that have been developed in our laboratory for the preparation of sulfoximines are described. Two of these involve the efficient, high yield oxidation of certain sulfilimines (iminosulfuranes) with ruthenium tetroxide (catalytic Ru0₂ + sodium periodate or hypochlorite cooxidant) and m-chloroperoxybenzoic acids, respectively, in biphasic systems. The third method is the direct preparation of sulfoximines from DMSO-t-butyl hypochlorite-aromatic amines. The scope and limitations of the procedures will be described.     

一种新型L-脯氨酸衍生的高效液相色谱手性固定相

设计和制备了一种用于手性化合物的高效液相色谱拆分的新型手性固定相（ＣＳＰ）。该固定相以构象刚性的Ｌ－脯氨酸为手性选择子,经引入保护基、萘酰胺化、加氢脱保护基、酰胺化和与ＬｉＣｈｒｏｓｏｒｂＮＨ２５μｍ微粒硅胶偶联等５步反应而制得。在此ＣＳＰ结构中引入萘酰胺,可增强ＣＳＰ和手性溶质之间的π－π相互作用,以提高该ＣＳＰ的对映体选择性。报道了４种Ｎ－３,５－二硝基苯甲酰－ＤＬ－氨基酸甲酯对映体色谱拆分的初步结果,对映体选择性在１．０４～１．１８之间。色谱拆分条件的优化和该固定相的应用将有待于进一步研究。     

新型手性脂质性酰胺型大环多胺配体的合成

酰胺型大环多胺同时具有大环多胺和寡聚肽(Ｏｌｉｇｏｐｅｐｔｉｄｅｓ)的结构特点 ,从而产生独特的物理化学性质 ,并且某些过渡金属配合物具有特殊的催化活性和生物功能 ,因而受到广泛关注和重视[1～ 6] 。它们在催化氧化、金属酶模型、分子识别和材料化学等方面已得到广泛的研究。然而 ,将手性引入酰胺型大环多胺形成手性酰胺型大环多胺的报道并不多见[7～1 1 ] 。近年来 ,我们报道了长链酰胺型大环多胺的合成以及构成的金属胶束超分子体系模拟水解金属酶[1 2 ,1 3] 。本文则以廉价的Ｌ 天门冬氨酸和Ｌ 谷氨酸为起始原料简便地合成了一类…     

A NEW METHOD FOR THE PREPARATION OF CARBONYL DIAZO COMPOUNDS

Azo compounds are very important in organic chemistry. In resent years, some notoworthy studies show that azobenzene derivatives possess very good optic remembering and photoelectric properties, optical switching and image storage by means of azobenzene liquid crystal film.^1,2 We have reported some new methods for the Azo compounds³. In this paper, We describe a new oxidation system KCIO₃/H₂SO₄ catalyzed by FeSO₄ to synthesis diazo compounds (ArN=NCON=NAr) in short time and good yield for the first time.     

手性化合物的萃取分离研究进展

综述手性化合物的萃取分离方法,包括亲合萃取分离、配位萃取分离、形成非对映体立体异构体萃取分离、离子交换反应萃取分离、反相胶团萃取分离以及膜萃取分离。中性氨基酸的萃取分离将会成为研究的热点。     

毛细电色谱法拆分安息香手性化合物

用毛细电色谱法成功地拆分了安息手性化合物,并获得了较好的重现性和分离度。     

THE PREPARATION OF CHIRAL SALICYLALDEHYDES BASED ON KAGAN'S ETHER

Two related routes to chiral salicylaldehydes which are derivatives of Kagan's ether have been developed. One route which is particularly simple begins with 2,6-diallylphenol. Facile conversion to a substituted benzofuran and assemblage of the basic framework of Kagan's ether is followed by an ozonolysis of the benzofuran ring to reveal the hydroxyaldehyde functionality characteristic of salicylaldehydes.     

手性二茂铁聚酰胺催化剂的合成及应用

以二茂铁为原料,经酰化、氧化和酰氯反应得到二茂铁二酰氯继而与手性二氨作用合成未见文献报道的三种新的手性二茂铁聚酰氨配体。其Ｒｈ（Ｉ）配合物催化苯乙酮的不对称氢转移化应应得到高的转化率,ｅ．ｅ．值１６．５％。新化合物的结构通过元素分析,核磁共振及红外光谱得到确证。     

一种制备勃姆石溶胶的新方法

以氯化铝为起始原料经离子交换过程制备勃姆石溶胶.该方法将阴离子交换树脂加入三氯化铝溶液中,提供OH-离子的同时可同步去除等量Cl-离子.应用TEM对溶胶胶粒结构进行了研究,采用XRD、FTIR对不同条件下制备的凝胶结构进行了分析,对制备勃姆石溶胶过程中的影响因素进行了探讨.结果表明,老化时间和溶液中Cl-离子浓度对产物的结构和性能有显着影响,Cl一离子完全去除后经老化可以获得稳定的勃姆石溶胶.等温氮气吸附结果显示,r氧化铝的比表面积随着老化时间的延长而下降.老化4h和16h后得到γ-氧化铝的比表面积分别为223.12m2/g和176.86m2/g.     

DESIGN OF POLYMER-SUPPORTED CHIRAL CATALYSTS

1INTRODUCTIONThesynthesisofopticallypurechiralcompoundshasgainedgreatimportance,particularlyintheareasofphannaceuticals,agrochemical,flavorsandfragrances[l].SeveraldifferentstrategiesareappliedtomanufactUreopticallypurechiralsubstrates.Amongthem,asymmetriccatalysisprovidespowerfulanduniqueadvantages,perhapstheforemostisthe"multiplicationofchirality",alargequantityofchiralproductcanbeproducedusingacatalyticamountofachiralsourceIZI.However,uptonowonlyafewprocesseshavemadethestepfromanacade…     

A ONE-STEP PROTOCOL FOR THE N-CHLOROMETHYLATION OF HETEROCYCLIC IMIDES

A convenient single step methodology for the N-chloromethylation of heterocyclic imides using a mixture of formaldehyde sodium bisulfite adduct and thionyl chloride is described.     

手性亚砜类化合物的包结拆分

本文简要综述了手性亚砜类化合物的包结拆分研究,介绍了吡啶亚砜类化合物（包括苯并咪唑类抗胃溃疡药物）的包结拆分研究的最近进展。     

THE PREPARATION OF NEW ISOFLAVONES

The synthesis of ten new isoflavones in good yield is described. The method, involving intermediate 2-hydroxybenzyl ketones, did not require protection of the hydroxyl groups of the starting polyphenols.     

希土离子不对称双氮杂冠醚配合物的合成、表征及CD谱

在乙醇中合成出三个希土硝酸盐与冠醚(+)-12,17-二乙基-1,4,7,10-四氧杂-13,16-二氮杂环十八烷(L)的配合物。经元素分析确定其组成为［Ln(NO₃)₂·L(+)］NO₃(Ln=La, Pr, Nd)。通过UV-VIS和FI-IR、电导测定等方法研究了配合物的配位结构和性质。测定并讨论了手性配合物［Pr(NO₃)₂·L(+)］NO₃的CD谱。     

β—环糊精衍生物手性固定相的研究及应用

合成了一种新的手性固定相２,６-Ｏ-二庚基-３-Ｏ三甲基硅烷基-β环糊精，以甲基苯硅油为稀释剂，采用快速超动态法，成功地制备了高效手性毛细管柱，考察了手性柱的色谱性能，分离了醇、酮、烯烃类等一些对映体。     

A NEW AND EFFICIENT SYNTHESIS OF INDENONE

Reaction of dichloroketone 2 with NEt₃ gave indenone (4) in high yield. Catodic reaction of 2 in the presence of C/Pt electrodes afforded the rearranged product 3 in high yield besides a small amount of chlorohydroxyketone 5. Reaction of rearranged dichloroketone 3 with NEt₃ provided indenone (4) as the sole product. The mechanism of these reaction was discussed.     

手性口恶唑硼烷酮催化不对称Aldol反应的研究

以廉价易得的手性氨基酸为原料合成了一系列氮磺酰化氨基酸配体,并将之与硼烷原闰制备成手性恶唑硼烷酮催化苯甲醛与烯醇硅醚的不对称Aldol反应,获得了较好的效果。对各种影响反应结果的因素进行了讨论,并对其不对称诱导机理进行了探讨。结果表明D-苯基甘氨酸衍生的手性恶唑硼烷酮催化剂对这种反应的催化效明显好于L-缬氨酸、L-亮氨酸、L-异亮氨酸等其它脂肪侧链氨基酸衍生的恶唑硼烷酮催化剂。其所得产物的化学产率和ee值分别为38.7%和81.7%。     

高效液相色谱手性固定相的制备及色谱柱的评价

制备了两种不同结构的β-环糊精型手性固定相CSP A和CSP B,制成手性色谱柱Ⅰ和Ⅱ,并且用DL-氨基酸衍生物的手性拆分实验对色谱柱进行了评价。     

STEREOSELECTIVE REACTIONS OF CHIRAL AMINES WITH RACEMIC CHLOROPHOSPHINES

Racemic chlorophosphines react stereoselectively with chiral l-phenylethylamines or amino acid esters to give diastereomerically enriched aminophosphines 3, which were isolated as diastereomerically pure crystalline borane complexes. Oxidation, thionation, the reaction with methyl iodide provide optically active derivatives of aminophosphines. (R,S)- and (S,S)-stereomers of phosphinic acid amides were separated by crystallization and a flash-chromatography. The stereochemical properties of phosphorus acid amides were investigated. The mechanism of asymmetric induction at the trivalent phosphorus atom was rationalized.