1-芳酰基-4-(1＇-N-β-D-吡喃型糖基)氨基硫脲类化合物的合成

通过2,3,4,6-四-O-乙酰基-β-D-吡喃型葡萄糖异硫氰酸酯和2,3,4-三-O-乙酰基-β-D-吡喃型木糖异硫氰酸酯与取代的芳基酰肼的亲核加成反应合成了10个1-芳酰基-4-(1＇-N-2＇,3＇,4＇,6＇-四-O-乙酰基-β-D-吡喃型葡萄糖基)氨基硫脲和7个1-芳酰基-4-(1＇-N-2＇,3＇,4＇-三-O-乙酰基-β-D-吡喃型木糖基)氨基硫脲,所得化合物的结构经元素分析,IR,1H NMR确证.     

3-烷基/芳基-6-(1''''-N-β-D-或-α-L-吡喃型全乙酰化糖基)- 均三唑并[3,4-b]-1,3,4-噻二唑的合成

通过2,3,4,6-四-O-乙酰基-β-D-吡喃型葡萄糖异硫氰酸酯(3)和2,3,4-三-O-乙酰基-α-L-吡喃型鼠李糖异硫氰酸酯(4)与3-烷基/芳基-4-氨基-5-巯基-1,2,4-三唑(5)在乙醇中回流,缩合得到了14个新的3-烷基/芳基-6-(1'-N-2',3',4',6'-四-O-乙酰基-β-D-吡喃型葡萄糖基或2',3',4'-三-O-乙酰基-α-L-吡喃型鼠李糖基)-均三唑并[3,4-b]-1,3,4-噻二唑类化合物(6a-6i,7a-7e),化合物结构经元素分析、IR和1H NMR确证.     

海枫藤中C21甾体苷的分离和结构测定

从萝摩科植物海枫藤[Marsdenia officinalis Tsiang et P.T.Li.]的藤茎中分离得到四个C21甾体去氧糖苷(1)～(4). 通过化学降解和波谱技术, 确定它们的化学结构依次为: 12-O-桂皮酰基-20-O-乙酰基(20S)-孕甾烷-6-烯-3β,5α,8β,12β,14β, 17β,20-庚醇 3-O-甲基-6-去氧-β-D-阿洛吡喃糖基-(1→4)-β-D-夹竹桃吡喃糖基-(1→4)-β-D-磁麻吡喃糖苷(1), 12-O-桂皮酰基-20-O-乙酰基(20S)-孕甾烷-6-烯-3β,5α,8β,12β,14β,17β,20-庚醇3-O-β-D-葡萄吡喃糖基-(1→4)-3-O-甲基-6-去氧-β-D-阿洛吡喃糖基-(1→4)-β-D-磁麻吡喃糖基-(1→4)-β-D-磁麻吡喃糖苷(2), 12-O-桂皮酰基-20-O-乙酰基(20S)-孕甾烷-6- 烯-3β,5α,8β,12β,14β,17β,20-庚醇3-O-β-D-黄夹吡喃糖基-(1→4)-β-D-磁麻吡喃糖基-(1→4)-β-D-磁麻吡喃糖苷(3), 12-O-烟酰基-肉珊瑚苷元3-O-β-D-葡萄吡喃糖基-(1→4)-3-O-甲基-6-去氧-β-D-阿洛吡喃糖基-(1→4)-β-D-夹竹桃吡喃糖基- (1→4)-β-D-磁麻吡喃糖基-(1→4)-β-D-磁麻吡喃糖苷(4). 其中1和2为新化合物, 分别命名为haifengtenoside A, haifengtenoside B, 3和4分别为已知化合物mucronatoside H 和 hainaneosides A, 系首次从该植物中分离得到.     

3-O-(β-D-吡喃葡萄糖-1-基)-6-(4-卤代苯基)哒嗪的合成与表征

利用6-(4-卤代苯基)-3(2H)-哒嗪酮的银盐(2)与2,3,4,6-四-O-乙酰基-1-溴-1-脱氧-α-D-吡喃葡萄糖(3)发生Koenigs-knorr反应, 合成了3-O-(2,3,4,6-四-O-乙酰基-β-D-吡喃葡萄糖-1-基)-6-(4-卤代苯基)哒嗪(4),4用干燥的氨气在0℃～-5℃下处理脱乙酰基保护基得相应的3-O-(β-D-吡喃葡萄糖-1-基)-6-(4-卤代苯基)哒嗪(5).其结构经元素分析,IR及1H NMR证实.     

黄芪属植物化学研究 II: 梭果萤芪花A和B的结构鉴定

本文从梭黄芪的干燥根中分得胡罗卜芪, β-谷甾醇和两个新黄芪皂芪A和B, 经光谱和化学方法确证, 芪A为3-O-[α-L-鼠李吡喃糖基(1→2)-β-D-木吡喃糖基]-25-O-β-D-葡萄吡喃糖基环黄芪醇花B为3-O-[α-L-鼠李吡喃糖基(1→2)-(3'-O-乙酰基)-β-D-木吡喃糖基]-25-O-β-D-葡萄吡喃糖基环黄芪醇。     

断节参甙的结构

从断节参根的粗甙中分离得到一个新甙——断节参甙(wallicoside,6).经光谱数据及降解反应证明其结构为告达庭-3-O-β-D-葡萄吡喃糖基-(1→4)-β-D-葡萄吡喃糖基-(1→4)-β-D-夹竹桃吡喃糖基-(1→4)-β-D-加拿大麻吡喃糖基-(1→4)-β-D-加拿大麻吡喃糖甙.     

3-D-（β-D-吡喃葡萄糖-1-基）-6-（4-卤代苯基）哒嗪的合成与表征

利用6-(4-卤代苯基)-3(2H)-哒嗪酮的银盐(2)与2，3，4，6-四-O-乙酰基-1-溴-1-脱氧-α-D-吡喃葡萄糖(3)发生Koenig’s-knorr反应，合成了3-0-(2，3，4，6-四-O-乙酰基-β-D-吡喃葡萄糖-1-基)-6-(4-卤代苯基)哒嗪(4)，4用干燥的氨气在0℃～-5℃下处理脱乙酰基保护基得相应的3-O-(β-D-吡喃葡萄糖-1-基)-6-(4-卤代苯基)哒嗪(5)。其结构经元素分析，IR及1H NMR证实。     

黄花棘豆化学成分的研究II:两种三萜皂苷的结构

从黄花棘豆的总皂苷中分离出两个新皂苷1和2.经光谱分析及化学方法确证,1为3-O-[α-L-鼠李吡喃糖基(1→2)-β-D-葡萄吡喃糖基(1→4)-β-D-葡萄吡喃糖醛酸基]-黄豆醇B;2为3-O-[α-L-鼠李吡喃糖基(1→2)-α-L-阿拉伯吡喃糖基(1→4)-β-D-葡萄吡喃糖醛酸基]-黄豆醇B.     

中药白头翁的皂苷 Ⅳ.主皂苷B_4和A_3结构的研究

白头翁皂苷B_4(1)经波谱及化学降解证实为双链苷,其结构为3(S),23-二羟基羽扇豆-20(29)-烯-28-酸的3-O-[α-L-吡喃鼠李糖基(1→2)-α-L-吡喃阿拉伯糖基]-28-O-[α-L-吡喃鼠李糖基(1→4)-β-D-吡喃葡萄糖基(1→6)]-β-D-吡喃葡萄糖酯苷。白头翁皂苷A_3(6)为与1具有相同3-O-糖链结构的单链苷。     

1-芳酰基-4-(1'-N-β-D-吡喃型糖基)氨基硫脲类化合物的合成

糖基硫脲;酰氨基硫脲;1-芳酰基-4-(1'-N-β-D-吡喃型糖基)氨基硫脲类化合物的合成     

Synthesis of 2,3-di-O-phytanyl-1-O-[glucosyl (galactosyl)-β(1→6) -mannosyl-α(1→2)-glucosyl-α (1→1)]-SN-glycerol. Purple membrane glycolipids

A convenient approach to the synthesis of triglycosyl-2,3-di-O-phytanyl-sn-glycerols will be presented. Special attention will be paid to the use of the following protective groups in carbohydrate chemistry: the 2,2,2-trichloroethoxycarbonyl, the 1,1,3,3-tetraisopropyldisiloxane-1,3-diyl and the o-dibromomethyl benzoyl group.     

Synthesis of polysaccharides. Communication 15. Synthesis of β-(1 → 6)-D-galactan

Conclusions 1,2-0-(1-exo-Cyano)ethylidene-3,4-di-0-acety1-6-0-trityl- and 1,2-0-(1-exo-cyano)ethylidene-3,4-di-0-benzoyl-6-0-trityl--D-galactopyranoses were synthesized. Their polycondensation led to D-galactans, which do not contain -glycoside bonds.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya., No. 10, pp. 2358–2363, October, 1984.     

Synthesis of α-(1→6)-D-mannane

Conclusions 1,2,-O-(1-Cyanoethylidene)-3,4-di-O-acetyl-6-O-trityl--D-mannopyranose was synthesized; after removal of the protecting groups, its polycondensation leads to-(16)-D-mannane with degree of polymerization 10.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1387–1390, June, 1981.     

Synthesis of O-(2-Acetamido-2-Deoxy-β-D-Glucopyranosyl)-(l→2)-O-α-D-Mannopyranosyl-(l→6)-O-β-D-Glucopyranosyl-(1→4)-2-Acetamido-2-Deoxy-D-Glucopyranose. A Potential Acceptor-Substrate for N-Acetylglucosaminyltransferase-V (GnT-V)

Abstract

The reaction of phenyl 3,4,6-tri-O-acetyl-2-deoxy-2-phthaIimido-l-thio-β-D-glucopyranoside with methyl 3,4,6-tri-O-benzyl-α-D-mannopyranoside catalysed by iodonium ion (TfOH-NIS) followed by deacylation-acetylarion afforded disaccharide 11. which was readily converted (in four steps) to bromide 12. A similar glycosylarion with phenyl 2,3,4,6-tetra-O-acetyl-l-thio-D-glucopyranoside of benzyl 2-acetamido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranoside 16 followed by O-deacetylation of the resulting intermediate gave disaccharide 18. The 4,6-O-benzylidene derivative of 18 was acetylated then deacetaled to give diol 21. This diol acceptor was condensed with bromide 12 (promoted by mercuric cyanide) to give the partially protected tetrasaccharide derivative 22 which was O-deacetylated and then subjected to catalytic hydrogenation to furnish the title tetrasaccharide 6. The structure assigned to 6 was supported by ¹H and ¹³C NMR spectral data and FAB mass spectroscopy.     

9-(β-D-2''-脱氧核糖基)-6-甲基嘌呤的合成

报道了9-(β-D-2'-脱氧核糖基)-6-甲基嘌呤合成的新方法.以肌苷1为原料,经酯化、氯化、氨解得6-氯嘌呤核苷(4),再经过羟基保护、6-位甲基化反应及脱保护反应得到关键中间体6-甲基嘌呤核苷7,用1,3-二氯-1,1,3,3-四异丙基二硅氧烷保护7核糖上的3,5-二羟基,2-羟基与苯氧基硫代甲酰氯反应后得到9,然后与氢化三正丁基锡[HSn(Bu-n)3]还原脱氧,最后脱保护得到目标化合物11.产物结构经MS,1HNMR,元素分析等鉴定.     

Synthesis of 3-aminopropyl glycosides of branched β-(1→3)-glucooligosaccharides

Russian Chemical Bulletin - The synthesis of branched β-(1→3)-glucooligosaccharides bearing a β-d-glucose residue at position 6 of one of the monosaccharides of the linear chain at...