摘要： This thesis investigates the application of chiral sulfoxides to the asymmetric synthesis of chiral amines and benzazepine alkaloids, the results are presented in four chapters. In Chapter 1, the addition of the anions of methyl phenyl sulfoxide and the novel methyl 2-methoxy-l-naphthyl sulfoxide to nitrones was shown to be a diastereoselective process under kinetically controlled conditions. The stereochemistry of these adducts was determine by chemical correlation with known p-amino sulfoxides. Chapter 2 is an extension of this method and describes the addition of lithiated methyl phenyl sulfoxide to oxaziridines. The relative stereochemistry of the major and minor adducts from these reactions was determined by 1H NMR spectroscopic analysis. A new method for the synthesis of oxaziridines by the oxidation of imines with Oxone® is also reported. In Chapter 3, an attempt was made to extend this methodology to the synthesis of β-amino sulfoxide (7), from the addition of methyl phenyl sulfoxide to nitrile oxides, benzohydroximinoyl chlorides and nitriles, and then reduction of the products by either sodium triacetoxyborohydride or sodium cyanoborohydride. However the diastereoselection of these reductions was poor. Chapter 4 deals with an attempt to solve the problems encountered with the synthesis of β-amino sulfoxide (2) in Chapters 1, 2, and 3. β-Keto 2- methoxy-1-naphthyl sulfoxides (1) were prepared and converted to β-amino sulfoxide (2) via a number of methods. These methods included reductive alkylation of (1) and the conversion of (1) to its β-sulfinyl enamine followed by diastereoselective reduction. Attempts to use the β-amino sulfoxide (2) for the synthesis of benzazepine alkaloids via a Pummerer type cyclization failed to give the expected product, however a novel rearrangement product was isolated and characterized.

关键词： 不对称合成   光学活性   消旋化   孤电子对   亚砜   化学工作者   化学合成方法   立体选择性   格氏试剂   环氧化  

摘要： 手性亚砜具有孤电子对,结构上呈锥形结构,由于R₁≠R₂,所以呈光学活性.又由于手性亚砜的消旋化能量和消旋温度较高（分别为146～176kJ/mol和200℃）,所以在反应过程中手性亚砜不易发生消旋化,是比较稳定的.虽然人们早已了解这一点,但是真正合成与应用手性亚砜还是七十年代才发展起来的.近年来,手性亚砜作为合成试剂,随着化学工作者对它研究的进一步深入和有机化学合成方法的不断创新与完善,它在有机合成特别是在不对称合成这一重要合成领域中的应用更加广泛。

关键词： 手性   铜催化剂   环丙烷羧酸酯   制备  

摘要： ３类手性配体ｄ－１０－樟脑磺酸及其衍生物，α－（－）－羟蒎酮及其衍生物，双唑啉衍生物分别与铜（Ⅱ）形成手性铜配合物，催化重氮乙酸酯与１，１－二苯乙烯或异丁烯的环丙烷化加成反应，得到光学活性环丙烷羧酸酯，不对称诱导最高可达９５％ｅ．ｅ．

关键词： .Recent advances   asymmetric hydroboration   scope   asymmetric reduction   successes   CHCH   Pure enantiomers   asymmetric homologation   crotylboration   boron route   Chiral organoboranes   general asymmetric synthesis   Fig Asymmetric  

摘要： Chiral organoboranes, readily available via asymmetric hydroboration or the Matteson asymmetric homologation reaction, have been successfully utilized for a general asymmetric synthesis of pure enantiomers. The recent continued successes achieved in our three-pronged approach to asymmetric synthesis - (1) asymmetric hydroboration, (2) asymmetric reduction, and (3) asymmetric allyl- and crotylboration, coupled with developments in asymmetric homologation, reveal the broad scope of these methodologies for the synthesis of stereoisomers in purities approaching 100 % ee.

摘要： New conditions were developed to allow nitrosoformates generated in situ by oxidation of N-hydroxycarbamates to undergo ene reactions with alkenes, then the asymmetric ene reactions of trans-2-phenylcyclohexanol nitrosoformate and several other chiral nitrosoformates were investigated. Diastereoselectivities of 1.4:1 to 7.2:1 were obtained in the ene reactions of trans-2-phenylcyclohexanol nitrosoformate with various alkenes. Conjugate addition reactions of enoate esters of trans-2-phenylcyclohexanol were investigated. Hydrolysis of the adducts provided chiral carboxylic acids of 84-96% e.e. The resolution of tetrahydropyranal acetals using trans-2-phenylcyclohexanol was investigated. A pair of diastereomeric bromides were resolved chromatographically and further reactions of the bromides were investigated. Trans-2-phenylcyclohexanecarboxylic acid was resolved using trans-2-phenylcyclohexanol. Asymmetric reactions using this acid as a chiral auxiliary were investigated and, when possible, compared to similar reactions using trans-2-phenylcyclohexanol.

摘要： Part I. In order to probe the applicability of arene-manganese complexes to the synthesis of ristocetin A, the synthesis of a protected ristomycinic acid was studied. The aryl ether bond was made under very mild conditions (0$\sp\circ$C, 1 h) and racemization of the arylglycine chiral center of the G-ring unit was not observed during phenoxide ion generation using sodium hydride. The glycine side chain was built using the Schollkopf bislactim anion. Racemization of the chiral center (G-ring unit) by this anion did not occur. However, the yield and diastereoselectivity of this reaction was low (8 $\sim$ 25%, 30 $\sim$ 60% d.e.). It was found that the use of an "aged" lithiated anion improves the yield, but this was also dependent on the method used for rearomatization of the dienyl manganese complexes. Dealkylation is a major reaction pathway with almost all oxidizing agents. With NBS in acetonitrile, the ratio of rearomatization:dealkylation was $\sim$9:1. Demetallation of the arene-manganese complex during the bislactim addition reaction was $\sim$10% (NMR). Following this analysis, yields of the bislactim addition/aromatization sequence were improved to 50%. The CFG ring moiety of ristocetin A was made using two different pathways and two different peptide cyclocoupling methods. From both pathways, two atropisomers were obtained. Cyclic dimer was not found in the reaction mixture and the structure of the two isomers were deduced from NMR NOESY experiments. None of the isomers exactly match to the structure of the CFG ring moiety of ristocetin A, but isomer 1.3.22a (minor product) is closely related to the desired conformation except for the orientation of the amide bond between C- and F-ring units. The yield of cyclization was better with the pathway A (19 and 22% for 1.3.22a and 1.3.22b, respectively) which forms the amide bond between the C- and F-ring units, and coupling by 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride was better than by using act

关键词： 不对称合成方法   合成研究   辅助物   反应温度   苯乙酸   芳香族羧酸   烷基   取代基  

摘要： α—烷基—α—羟基苯乙酸的不对称合成研究王大升，恽榴红（军事医学科学院毒物药物研究所）对三种不同的不对称合成方法进行了研究，系统地考察了α－烷基－α－羟基苯乙酸的不对称合成方法，研究了手性辅助物的合成，不对称诱导机制，有机锌试剂的反应性能，反应温度和...

关键词： 樟脑   硫亚胺   不对称合成   手性胺  

摘要： 合成了四种含樟脑巯基手性助剂的光学活性的硫亚胺化合物。

关键词： 金鸡纳碱   化合物   不对称合成   催化   鎓盐  

摘要： 本文介绍了金鸡钠碱及其鎓盐作为催化剂催化的一些反应,这些反应包括C-C,C-P,C-S键的形成.本文还讨论了催化反应的特点及催化剂结构与催化活性之间的关系,金鸡纳碱催化属于一般的不对称诱导催化,而其鎓盐则属于不对称相转移催化.

摘要： This thesis is presented in two parts. Part 1. Asymmetric Synthesis via Chiral Sulfoximines. Chapter 1. Asymmetric Synthesis of Chiral Alcohols and Ketones from Sulfoximines The application of chiral sulfoximines to the asymmetric synthesis of chiral alcohols and ketones is described historically in Chapter 1. Chapter 2. Asymmetric Synthesis of Chiral Alcohols and Chiral Ketones from (+)-(S)-N-t- B u t y l d i p h e n y l s i l y l - S - M e t h y l - S-Phenylsulfoximine. The synthesis and applications of (+)-(S)-N-t-butyldiphenylsilyl- S-methyl-S-phenylsulfoximine to the asymmetric synthesis of chiral alcohols is described in Chapter 2. The diastereoselectivities of all these reactions have been documented. The stereochemistry of some major adducts was determined by X-ray crystallography. Two racemic ketones, 2-tbutyl- cyclohexanone and 2-methyl-cyclohexanone were successfully resolved by diastereoselective addition of lithiated (+)-(S)-N-t-butyldiphenylsilyl-S-methyl-S-phenylsulfoximine, followed by separation of the diastereomeric adducts and then thermolysis. Chapter 3. Diastereoselective Conjugate Addition Reactions of Lithiated Allylic Sulfoximine to Cyclic and Acyclic Enones. The asymmetric conjugate addition reactions of racemic S-allyl S-phenyl-N-tosylsulfoximine with Michael acceptors and carbonyl compounds is described in Chapter 3. The diastereoselective ratio of all reactions have been documented. The stereochemistry of two major adducts was determined by Xray crystallography analysis. Part 2. Diasteroselective Synthesis of p-Azido Sulfoxides. Chapter 4. Addition of Nitrogen Nucleophiles to Vinyl Sulfoxides. A survey of the conjugate addition reactions of vinyl sulfoxides with nitrogen nucleophiles is described. Chapter 5. Addition of Azide to Vinyl Sulfoxides. The conjugate addition reaction of azide ion to p - a r y l - a - phenylsulfinylacrylates is reported in Chapter 5. Reactions in the presence of acetic acid gives triazoles while reactions in the