6,6'-取代1,1'-联二萘酚衍生的手性磷酸的合成

1,1'-联二萘酚(1)经溴代反应制得6,6'-二溴-1,1'-联二萘酚(2);2经苄基保护羟基制得2,2'-二苄氧基-6,6'-二溴-1,1'-联二萘(3);3经Ullmann缩合在6,6'-位引入甲氧基制得2,2'-二苄氧基-6,6'-二甲氧基-1,1'-联二萘(4b);3经Kumada偶联反应在6,6'-位引入正己基制得2,2'-二苄氧基-6,6'-二正己基-1,1'-联二萘(4c);4b和4c经还原脱去苄基制得6,6'-位取代1,1'-联二萘酚(5b和5c);2,5b和5c分别与三氯氧磷反应合成了3种1的6,6'-位取代手性磷酸(6a~6c),其结构经1H NMR和31P NMR表征。其中6c为新化合物。     

聚[(S)-3-乙烯基-2,2'-二羟基-1,1'-联萘]的钛配合物催化三乙基铝对醛的不对称加成反应

通过维蒂希反应合成了(S)-3-乙烯基-2,2'-甲氧甲氧基-1,1'-联萘.将单体(S)-3-乙烯基-2,2'-甲氧甲氧基-1,1'-联萘用偶氮二异丁腈作引发剂进行自由基聚合得到了聚[(S)-3-乙烯基-2,2'-二甲氧基甲氧基-1,1'-联萘].该聚合物上的MOM保护基通过酸脱除获得手性螺旋聚合物聚[(S)-3-乙烯基-2,2'-二羟基-1,1'-联萘].将手性螺旋聚合物聚[(S)-3-乙烯基-2,2'-二羟基-1,1'-联萘]与Ti(O-i-Pr)4形成的配合物应用于三乙基铝与醛的不对称加成反应中,获得了较好的对映选择性,ee值最高为85%.更重要的是,这种聚合物还可以被回收利用多次且催化活性没有明显降低.     

含(R)或(S)-1,1''''-联萘和噁二唑单元的手性高分子合成与性质研究

在Pd(PPh3)4催化下, 将单体(S)-6,6'-二溴-2,2'-二正丁氧基-1,1'-联萘[(S)-M-1]和(R)-6,6'-二溴-2,2'-二正丁氧基-1,1'-联萘[(R)-M-1]分别与2,5-二(4-三正丁基锡基苯)-1,3,4-噁二唑(M-2)通过Stille交叉耦合反应合成了手性高分子P-1与P-2, 并用 1H NMR、 13C NMR、 FTIR、 UV、热分析、荧光光谱、 GPC和CD等分析方法进行了表征. 手性高分子P-1和P-2都能发射较强的蓝色荧光; 在高分子侧链上引入丁氧基后使得手性高分子的溶解性能增强, 并具有良好的成膜性能; 在高分子主链引入亲电子的噁二唑生色团能使其特别适合于作为空穴电子传输层, 对氧和热特别稳定, 是一类潜在的光电高分子材料.     

含(R)或(S)-1,1'-联萘和噁二唑单元的手性高分子合成与性质研究

在Pd(PPh3)4催化下,将单体(S)-6,6'-二溴-2,2'-二正丁氧基-1,1'-联萘[(S)-M-1]和(R)-6,6'-二溴-2,2'-二正丁氧基-1,1'-联萘[(R)-M-1]分别与2,5-二(4-三正丁基锡基苯)-1,3,4-噁二唑(M-2)通过Stille交叉耦合反应合成了手性高分子P-1与P-2,并用1HNMR、13CNMR、FTIR、UV、热分析、荧光光谱、GPC和CD等分析方法进行了表征.手性高分子P-1和P-2都能发射较强的蓝色荧光;在高分子侧链上引入丁氧基后使得手性高分子的溶解性能增强,并具有良好的成膜性能;在高分子主链引入亲电子的噁二唑生色团能使其特别适合于作为空穴电子传输层,对氧和热特别稳定,是一类潜在的光电高分子材料.     

螺旋聚[(S)-3-(二苯羟甲基)-3′-乙烯基-2,2'-二羟基-1,1'-联萘]的合成、光学性质及其在杂-Diels-Alder反应中的不对称诱导

合成了一种基于联萘酚的新型手性单体,(S)-3-(二苯羟甲基)-3'-3-乙烯基-2,2'-二羟基-1,1'-联萘(5).通过由偶氮异丁腈(AIBN)引发的自由基聚合得到聚[(S)-3-(二苯羟甲基)-3'-3-乙烯基-2,2'-二羟基-1,1'-联萘](P-5),旋光、紫外-可见光谱、圆二色谱表征结果表明P-5以单手性螺旋结构的形式存在于溶液中.考察了螺旋齐聚物P-5在催化苯甲醛与Danishefsky双烯烃的杂-Diels-Alder(HDA)反应中的不对称诱导作用,所得加和产物的ee值达71%,P-5可以被回收重复使用而保持催化活性不变.     

手性相转移催化剂的合成及其在氨基酸烷基化反应中的应用

以2-叔丁基-5-甲基苯酚为原料,经4步反应制得2,2'-二甲基-3,3'-取代基-4,4'-二甲氧基-5,5'-二叔丁基-1,1'-联苯(6a~6g);6经溴化反应制得2,2'-二溴甲基-3,3'-取代基-4,4'-二甲氧基-5,5'-二叔丁基-1,1'-联苯(7a~7g);7与(R)-(+)-N-甲基-1-(1-萘基)乙基胺经环合反应合成了7种具有联苯结构的手性相转移催化剂(9a~9g)。6f,6g,7f,7g,9f和9g为新化合物,其结构经1H NMR,13C NMR和MS表征。以N-二苯基亚甲基甘氨酸叔丁酯的不对称烷基化为探针反应,考察了9a~9g的催化活性。结果表明:在催化剂用量为1mol%时,9g的催化性能最好,产率和对映选择性分别为80%和70%。     

1,1-二苯基(或4,4'-二溴二苯基)-3-(3-三乙氧基硅基)丙基脲的合成

以三乙胺为缚酸剂,二苯胺和4,4'-二溴二苯胺分别与三光气反应制得N,N-二苯基氨基甲酰氯(2a)和N,N-(4,4'-二溴二苯基)氨基甲酰氯(2b);2a和2b分别与3-氨丙基三乙氧基硅烷反应合成了两个新型的含非对称取代脲的功能性有机硅氧烷——1,1-二苯基-3-(3-三乙氧基硅基)丙基脲和1,1-(4,4'-二溴二苯基)-3-(3-三乙氧基硅基)丙基脲,其结构经1H NMR,13C NMR和IR表征。     

新型手性季鏻盐的合成

以(S)-联萘酚为原料,与三氟甲磺酸酐反应制得联萘酚三氟甲磺酸酯(2);2在Ni(dppp)Cl2催化下与碘甲烷格氏试剂反应得2,2’-二甲基联萘(3);3经溴代反应得2,2’-二溴甲基联萘4;4与1,3-双(二苯基膦)丙烷(dppp)在甲苯中回流合成了一个新型的联萘酚衍生的双中心手性季鏻盐,其结构经1H NMR,31P NMR和FT-IR表征。     

2-{[(2'-氰基联苯基-4-基)甲基]氨基}-3-硝基苯甲酸甲酯的合成

以3-硝基-2-氨基苯甲酸甲酯为原料,经三氟乙酰化、N-烷基化和脱保护反应制得坎地沙坦中间体2-{[(2'-氰基联苯基-4-基)甲基]氨基}-3-硝基苯甲酸甲酯,其结构经~1H NMR,~(13)C NMR和MS(ESI)确证。     

聚[(S)-3-丙烯酰胺基-2,2'-二羟基-1,1'-联萘]的合成及催化二乙基锌与芳基醛不对称加成反应中的应用

通过自由基聚合得到聚[(S)-3-丙烯酰胺基-2,2'-二羟基-1,1'-联萘](poly-6),并将其应用于芳基醛和二乙基锌(Et2Zn)的不对称加成反应中.反应具有较好的对映选择性,ee值最高可达95%,且poly-6可以被回收重复使用6次保持催化活性基本不变.     

对称-3,3'-二(取代苯基氨基)-4,4'-二(氨基)-5,5'-(1,4-丁二基)-1,2,4-三唑的合成

以己二酸为原料,经酯化、肼解后与异硫氰酸苯酯(或对氯异硫氰酸苯酯)反应合成了两个新化合物——对称-N1,N1'-(1,4-丁二基)二(甲酰胺基)-N4,N4'-二(取代苯基)硫脲(3a和3b);3a和3b分别经肼解合环合成了两个新化合物——对称-3,3'-二(取代苯基氨基)-4,4'-二(氨基)-5,5'-(1,4-丁二基)-1,2,4-三唑,其结构经1H NMR,IR和元素分析表征。     

Microbiological transformations—XII: Microbiological reduction of racemic 1-(2',2',3'-trimethyl-cyclopent-3'-en-1'-yl)propan-2-one and 1-(2',2',3'-trimethyl-cyclopent-3'-en-1'-yl)butan-2-one by rhodotorula mucilaginosa

The microbiological reduction of (±)-l-(2',2',3'-trimethylcyclopent-3'-en-l'-yl)-propan-2-one (4) and (±)-1-(2',2',3'-trimethylcyclopent-3'-en-l'-yl)-butan-2-one (5) by Rhodotorula mucilaginosa was investigated. Both enantiomers of 4 are reduced stereospecifically to corresponding alcohols; (+)-(2S, l'R)-(2',2',3'-trimethylcyclopent-3'-en-l'-yl)-propan-2-ol (6) and (-)-(2S,l'S)-(2',2',3'-trimethylcyclopent-3'-en-l'-yl)-propan-2-ol (7). p ]The substrate selectivity in the reduction of 5 was observed: R enantiomer of 5 yields stereospecifically (+)-(2S,1'R)-(2',2',3'-trimethylcyclopent-3'-en-l'-yl)-butan-2-ol (8) while S(-)5 remains unchanged.     

一种吲哚螺吡咯多取代杂环化合物的合成及其晶体结构

利用多组分1,3偶极环加成反应方法,合成了一种新的螺环结构1'-甲基-3'-吡啶甲酰基-4'-(2-噻吩基)螺[吲哚啉-3,2'-吡咯啉]-2-酮化合物,并对该化合物进行了红外光谱、核磁共振谱及X-射线单晶衍射表征.单晶衍射结果表明:该晶体属于三斜晶系,空间群为P-1,晶体参数为a=0.899 9(1)nm,b=0.914 4(1)nm,c=1.271 1(2)nm,α=92.852(1)°,β=107.305(2)°,γ=101.580(1)°.在分子晶体结构中,吡咯啉环采用了信封式构象,通过螺碳原子与吲哚啉环相连,形成刚性螺环结构,2个环接近垂直构型,其二面角为84.15(2)°.     

2'-deoxyribonucleoside 3'-aryl phosphoranilidates: Key intermediates in the stereospecific synthesis of 2'-deoxyribonucleoside cyclic 3',5'-phosphorothioates and dinucleoside(3'→5')-phosphoranilidates

Phosphorylation of the 5'-O-monomethoxytrityl-2'-deoxyribonucleosides by means of aryl phosphoranilidochloridates gives the diastereoisomers of 5'-O-monomethoxytrityl-2'-deoxyribonucleoside 3'-aryl phosphoranilidates. Their separation can be performed by means of chromatographic techniques. They can be further converted to the 2'-deoxyribonucleoside cyclic 3'-5' phosphoranilidates, which are intermediates in the stereospecific synthesis of 2'-deoxyribonucleoside cyclic (3'-5')phosphorothioates of known absolute configuration at phosphorus.     

Studies on the syntheses of heterocyclic compounds—DCCLXII : Alternative synthesis of trans-3-(1'R*-hydroxyethyl)-4-(2',2'-dimethoxyethyl)-2-azetidinone,a synthetic intermediate of thienamycin

Synthesis of trans-3-(1'R^*-hydroxyethyl)-4-(2',2'-dimethoxyethyl)-2-azetidinone (5), an important intermediate for the synthesis of thienamycin (1), was investigated starting from the isoxazoline derivatives 3 and 9. The most effective method was catalytic hydrogenation of trans-4-t-butoxycarbonyl-3-(2,2'-dimethoxyethyl)-5-methyl-isoxazoline (9) with Adams catalyst in acetic acid, followed by trimethylsilylation of the resulting epimeric aminoesters 11A and B, cyclization with EtMgBr, and deblocking. Novel reductions of the isoxazolines with sodium borohydride and nickel chloride or with diborane followed by catalytic hydrogenation were also reported.     

1H-NMR-spektroskopische konformationsanalyse von halogenierten thymidinabkömmlingen: I. konformation von thymidin, 3',5'-didesoxy-3'-chlor-5'-fluor-thymidin und 3', 5'-didesoxy-3',5'-difluor-thymidin

An improved method is given for determining the conformation of furanoid nucleosides by ¹H-NMR-spectra analysis using halogen-substituted thymidines as examples. The state of the three equilibria - ring-puckering, rotation about the C₄-C₅- bond and about the glycosidic bond - are influenced by the halogen substituents. Compared with thymidine the 3'-chlorine substituent shifts the furanose conformation to conformers, where the 3'-chlorine substituent is equatorial. The 5'-fluorine substituent increases the contribution of the G-G-rotamer and the ratio of syn-conformation. The relationships between the conformers in the pseudo-rotatory cycle and the population of the C_4'-C_5' rotamers are discussed.     

An efficient synthesis of certain 5-substituted-2'-deoxyuridine 3',5'-cyclic monophosphate p-o-alkyl(aralkyl) esters. The crystal and molecular structure of 5-IODO-2'-deoxyuridine 3',5'-cyclic monophosphate p-o-methyl ester with axial methoxy group

Some 5-alkyl- and 5-halogeno-2'-deoxyuridine 3',5'-cyclic mono- phosphate P-O-alkyl(aralkyl) esters have been prepared from the silver salts of the parent cyclic monophosphates and alkyl(aralkyl) iodides. The diastereomeric phosphotriesters have been characterized by spectroscopic methods. The crystal and molecular structure of 5-iodo-2'-deoxyuridine 3',5'-cyclic monophosphate P-O-methyl ester with axial methoxy group has been determined. We failed to obtain the desired triesters from the reactions of the cAMP silver salt with alkyl iodides, contrary to previous claims in the literature.