关键词： 脂肪酶   酯氨解反应   不对称合成   光学纯药物  

摘要： 脂肪酶催化的新反应—酯氨解反应 (羧酸可以在脂肪酶作用下形成酯 ,然后在同一酶作用下进行酯氨解反应 ) ,不仅是合成手性酰胺的一个非常有用的方法 ,而且也是手性羧酸及手性醇动力学拆分的有效途径。通过比较脂肪酶催化几种外消旋酯水解、转酯及氨解反应 ,得出脂肪酶催化酯氨解反应在制备光学纯化合物中将有广阔的应用前景这一结论。

关键词： 手性   不对称合成   不对称催化   精细化工  

摘要： 综述了不对称催化的进展及其在精细化工中的应用情况

关键词： 手性金属催化剂   环丙烷   不对称合成  

摘要： 手性金属催化剂在不对称环丙烷化反应中的应用一直是不对称合成领域的一个热点。对三十多年来的这一领域的手性金属催化剂的发展作了详细的归纳和评述。

关键词： 手性药物   拆分分离   手性库   不对称合成   抗生素  

摘要： 对映异构体药物由于空间立体构型不同而在体内往往呈现很大的药理学等方面的差异。采用手性技术开发生产手性药物已成为世界制药工业的发展潮流。本文从拆分分离技术、手性库技术和不对称合成三个方面介绍了手性技术在抗生素等药物生产中的应用。

关键词： 1,1'-联-2-萘酚   外消旋   拆分   不对称合成  

摘要： 综述了外消旋 1 ,1′-联 -2 -萘酚拆分方法学研究进展 ,包括环磷酸酯法、羧酸酯法、碳酸酯法、环状醚法、环硼酸酯法、包合物结晶法、酶水解法。并对现有的各种拆分方法作出评价。

关键词： allylations   amines   asymmetric synthesis   Grignard reactions   zinc  

摘要： The diimine prepared by condensation of glyoxal trimer dihydrate with (S)-1-phenylethylamine underwent double addition of allylic zinc compounds (2-butenyl-, 2,4-pentadienyl-, 2-methyl-2-propenylzinc bromide) in THF generally at -78 degrees C, with allylic inversion. The newly formed stereocentres adjacent to the nitrogen atoms had prevalently the R configuration. Removal of the auxiliary from the secondary 1,2-diamines with concomitant hydrogenation of the C=C double bonds afforded the primary 1,2-diamines. The reaction with 3-methyl-2-butenylzinc bromide gave almost exclusively the a-amino imine from which the a-aminoaldehyde was obtained by hydrolysis. On the other hand, 3-methyl-2-butenylmagnesium chloride reacted at 0-20 degrees C to give the diamine with linear-chain substituents, owing to the reversibility of the organometallic addition.

关键词： asymmetric synthesis   triflic anhydride   iminium salts   tandem reactions   Michael additions  

摘要： Reaction of N-methacryloyl SMP - triflic anhydride complex (2) with secondary aromatic amines followed by hydrolysis gives enantiomerically enriched (up to 81% ee) tetrahydroquinolinones 4a-f in moderate yields. The absolute configuration of 4f was established by an X-ray structure determination

关键词： asymmetric synthesis   tetrahydroisoquinolines   Bischler-Napieralski reaction   diastereoselective alkylation of amides phenylglycinol  

摘要： Bischler-Napieralski cyclisation of optically active beta-substituted phenylethylamines 4a-c followed by diastereoselective reduction led to 1,4-disubstituted tetrahydroisoquinolines 6a-c and 8a-c. The same methodology afforded the 4-benzyl pyrroloisoquinolines 10.

关键词： dihydroxylation   birch reduction   allylic oxidation   iodolactonization   Claisen rearrangement   CP compounds   total synthesis  

摘要： An enantioselective approach to construction of the complex framework of the CP compounds is presented. The synthesis relies on initial elaboration of the two sidechains. The "upper" appendage was asymmetrically dihydroxylated with both AD-mix reagents in order to lend flexibility to the scheme and provide the necessary handle for evolving the additional stereogenic centers. These fragments were linked to benzoic acid via Birch reduction-alkylation and subsequent cuprate addition. A series of functionalization reactions including dissolving metal reduction, Claisen rearrangement, iodolactonization, regioselective epoxide cleavage-oxidation, and intramolecular Wadsworth-Emmons cyclization took advantage of highly efficient stereocontrol. However, this flexibility was thwarted when deprotonation of a penultimate intermediate failed to be regioselective in the proper direction.

关键词： 苯衍生物/化学   雌激素拮抗剂/化学合成   指示剂和试剂   分子构象   有机金属化合物   脯氨酸/类似物和衍生物   立体异构现象   他莫昔芬/类似物和衍生物   他莫昔芬/化学合成  

摘要： Dirhodium tetrakis(S(N-dodecylbenzenesulfonyl)prolinate) (Rh-2(S-DOSP)(4))-catalyzed decomposition of methyl phenyldiazoacetate in the presence of 1,1-diarylethylenes results in intermolecular cyclopropanation with high enantioselectivity (up to 99% ee) and moderate diastereoselectivity (up to 80% de). The reaction was applied to the asymmetric synthesis of a cyclopropyl analogue of tamoxifen.