3,4-di-O-acetyl-2,6-dideoxy-2-fluoro-α-L-talopyranosyl bromide | 103930-49-0

• 分子结构分类: 有机化合物
• 英文名称: 3,4-di-O-acetyl-2,6-dideoxy-2-fluoro-α-L-talopyranosyl bromide
• 英文别名: 3,4-di-O-acetyl-2,6-dideoxy-2-fluoro-α-L-talopyranosyl-bromide；[(2S,3R,4R,5R,6S)-4-acetyloxy-6-bromo-5-fluoro-2-methyloxan-3-yl] acetate
• CAS: 103930-49-0
• 化学式: C₁₀H₁₄BrFO₅
• 分子量: 313.121
• InChiKey: CIHHIEKFXWQBMO-DMGYWXMPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3,4-di-O-acetyl-2,6-dideoxy-2-fluoro-α-L-talopyranosyl bromide 在 sodium hydroxide 、 溴 、 mercury dibromide 、 mercury(II) oxide 作用下， 以 1,4-二氧六环 、 甲醇 、 二氯甲烷 为溶剂， 反应 28.0h， 生成 (8S,10S)-8-(2-Bromo-1,1-dimethoxy-ethyl)-10-((2R,3R,4R,5S,6S)-3-fluoro-4,5-dihydroxy-6-methyl-tetrahydro-pyran-2-yloxy)-6,8,11-trihydroxy-1-methoxy-7,8,9,10-tetrahydro-naphthacene-5,12-dione
  参考文献：
  名称：

  抗肿瘤活性的7-O-（2,6-二脱氧-2-氟-α-L-talopyranosyl）-柔红霉素和-adriamycinone的合成。

  摘要：

  标题化合物（17和23）是通过将3，4-二-O-乙酰基-2，6-二脱氧-2-氟-α-L-塔拉吡喃糖基溴化物（15）与柔红霉素偶联而制备的。制备15的关键步骤是在乙二醇中用KHF2将2,3,3-脱水-4-O-苄基-6-脱氧-α-L-瓜吡喃糖苷甲基的环氧化物开环，然后将2-氟-获得了L-吡喃吡喃糖苷。化合物17和23显示出强的抗肿瘤活性。

  DOI：

  10.1016/0008-6215(87)80243-4
• 作为产物：
  描述：

  1,3,4-tri-O-acetyl-2,6-dideoxy-2-fluoro-α-L-talopyranose 在 溴化钛(IV) 作用下， 以 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 22.0h， 以95%的产率得到3,4-di-O-acetyl-2,6-dideoxy-2-fluoro-α-L-talopyranosyl bromide
  参考文献：
  名称：

  抗肿瘤活性的7-O-（2,6-二脱氧-2-氟-α-L-talopyranosyl）-柔红霉素和-adriamycinone的合成。

  摘要：

  标题化合物（17和23）是通过将3，4-二-O-乙酰基-2，6-二脱氧-2-氟-α-L-塔拉吡喃糖基溴化物（15）与柔红霉素偶联而制备的。制备15的关键步骤是在乙二醇中用KHF2将2,3,3-脱水-4-O-苄基-6-脱氧-α-L-瓜吡喃糖苷甲基的环氧化物开环，然后将2-氟-获得了L-吡喃吡喃糖苷。化合物17和23显示出强的抗肿瘤活性。

  DOI：

  10.1016/0008-6215(87)80243-4

文献信息

• L-talopyranoside derivatives and process for the preparation of same
  申请人：Dong-A Pharmaceutical Co., Ltd.

  公开号：US05374746A1

  公开（公告）日：1994-12-20

  The present invention relates to a L-talopyranoside derivative of the formula (I): ##STR1## wherein, A is hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms, or a hydroxyl-protecting group; B.sub.1 and B.sub.2, the same or different from each other, are independently hydrogen atom or a hydroxyl-protecting group; R.sub.1 and R.sub.2 may form a alkylene group with a carbon atom of 5-position of the sugar skeleton, or one of them is hydrogen atom and the other is CH.sub.2 X wherein, X is hydrogen, or a protected or un-protected hydroxyl group. Provided that, the following compounds are excepted: ##STR2## wherein, B.sub.1 and B.sub.2 are independently hydrogen atom or acetyl. L-talopyronoside derivatives of the present invention is a very useful intermediate for the synthesis of anthracycline antibiotics having an antitumor activity. The process according to the invention has an advantage of significant reduction in the production cost and therefore expected to be very useful for the preparation of anthracycline antibiotics in an industrial scale.

  本发明涉及一种L-塔洛吡喃糖苷衍生物，其结构式如式(I)所示：##STR1##其中，A为氢原子、含有1至5个碳原子的低级烷基或羟基保护基；B1和B2彼此相同或不同，各自独立地为氢原子或羟基保护基；R1和R2可以与糖骨架5位上的碳原子形成亚烷基，或者其中之一为氢原子，另一个为CH2X，其中X为氢，或保护或未保护的羟基。但以下化合物除外：##STR2##其中，B1和B2各自独立地为氢原子或乙酰基。本发明的L-塔洛吡喃糖苷衍生物是合成具有抗肿瘤活性的蒽环类抗生素的非常有用的中间体。根据本发明的工艺具有显著降低生产成本的优点，因此预计在工业规模制备蒽环类抗生素方面非常有用。
• Synthesis of a Potent Rhodomycin, Oxaunomycin, and Its Analogs.
  作者：Yasuyuki KITA、Hiroshi MAEDA、Masayuki KIRIHARA、Yuji FUJII、Toyokazu NAKAJIMA、Hirofumi YAMAMOTO、Yasumitsu TAMURA、Hiromichi FUJIOKA

  DOI：10.1248/cpb.40.61

  日期：——

  Oxaunomycin (3) and its regioisomer (6) were synthesized by employing regioselective glycosidations of te C-7 hydroxyl group of 10-O-acetyl-β-rhodomycinone (16) and the C-10 hydroxyl group of the C-7, 9-O phenylboronate (14), respectively, in the presence of trimethylsilyl trifluoromethanesulfonate. Under the Konigs-Knorr conditions, 16 was also glycosidated to provide a fluoro sugar analog (7).

  Oxaunomycin（3）及其区域异构体（6）通过采用选择性地对10-O-乙酰-β-红霉素酮（16）的C-7羟基和C-7, 9-O-苯基硼酸酯（14）的C-10羟基进行糖苷化反应合成，反应中使用了三甲基硅基三氟甲基磺酸盐。在Konigs-Knorr条件下，16也进行了糖苷化反应，得到了一种氟糖类似物（7）。
• 2,6-Dideoxy-2-fluoro-L-talopyranose and derivates thereof and the production of these compounds
  申请人：ZAIDAN HOJIN BISEIBUTSU KAGAKU KENKYU KAI

  公开号：EP0230322A2

  公开（公告）日：1987-07-29

  2.6-Dideoxy-2-fluoro-L-talopyranose and I-substituted denvatives thereof. including methyl 2.6-dideoxy-2-fluoro-L-talopyranoside and 3.4-di-O-protected-2,6-dfdeoxy-2-fluoro-L-ta- lopyranosyl halides. are now provided and these new compounds are useful as intermediates for use in the synthesis of new compounds having antitumor activity. especially 7-O-(2.6-dideoxy-2-fluoro-α-L-talopyranosyl)daunomycinone or -adriamycinone. 2.6-Dideoxy-2-fluoro-L-talopyranose shows antibacterial activity. 2.6-Dideoxy-2-fluoro-L-talopyranose and the I-substituted derivatives thereof may be produced by a multi-stage process starting from L-fucose.

  2.6-二脱氧-2-氟-L-talopyranose 及其 I-取代的变性物，包括甲基 2.6-二脱氧-2-氟-L-talopyranoside 和 3.4-二-O-保护-2,6-二脱氧-2-氟-L-talopyranosyl 卤化物。特别是 7-O-(2.6-二脱氧-2-氟-α-L-吡喃塔吡喃糖基)daunomycinone 或-adriamycinone。2.6-Dideoxy-2-fluoro-L-talopyranose 具有抗菌活性。2.6-Dideoxy-2-fluoro-L-talopyranose 及其 I-取代衍生物可从 L-岩藻糖开始通过多级工艺生产。
• New anthracycline derivatives and processes for the preparation of the same
  申请人：ZAIDAN HOJIN BISEIBUTSU KAGAKU KENKYU KAI

  公开号：EP0335369A2

  公开（公告）日：1989-10-04

  As new anthracycline derivatives are now produced 7-O-(2,6-dideoxy-2-fluoro-a-L-mannopyranosyl)-daunomycinone and -adriamycinone, their 4-demethoxy derivatives and 14-0-ester derivatives of the adriamycinone compounds of them, as well as 4-demethoxy-7-0-(2,6-dideoxy-2-fluoro-α-L-talopyranosyl)-daunomycinone and -adriamycinone and 14-0-ester derivatives of the adriamycinone compound thereof which )exhibit excellent antitumor activities and are useful as antitumor agents. These new anthracycline derivatives may be produced by various processes.

  作为新的蒽环类衍生物，现已生产出 7-O-(2,6-二脱氧-2-氟-a-L-吡喃甘露糖基)-大诺霉素酮和-阿霉素酮、它们的 4-去甲氧基衍生物和阿霉素酮化合物的 14-0 酯衍生物、以及 4-去甲氧基-7-0-(2,6-二脱氧-2-氟-α-L-吡喃木糖基)-daunomycinone 和-adriamycinone 及其阿霉素酮化合物的 14-0-ester 衍生物，这些衍生物具有优异的抗肿瘤活性，可用作抗肿瘤药物。这些新的蒽环类衍生物可以通过各种工艺生产。
• Novel anthracycline derivatives having 4-amino-2,4,6-trideoxy-2-fluoro-alpha-L-talopyranosyl group
  申请人：ZAIDAN HOJIN BISEIBUTSU KAGAKU KENKYU KAI

  公开号：EP0848010A1

  公开（公告）日：1998-06-17

  7-O-(4-Amino-2,4,6-trideoxy-2-fluoro-α-L-talopyranosyl)-daunomycinone or -adriamycinone is now synthesized as a novel daunomycinone or adriamycinone derivative having the general formula wherein R is a hydrogen atom or hydroxyl group. These novel compounds according to this invention exhibit excellent antitumor activities and have a high solubility in water, and hence they are useful as an antitumor agent.

  7-O-(4-氨基-2,4,6-三脱氧-2-氟-α-L-吡喃他酰胺基)- daunomycinone 或-adriamycinone 现被合成为具有通式的新型 daunomycinone 或 adriamycinone 衍生物。 其中 R 为氢原子或羟基。根据本发明的这些新型化合物具有优异的抗肿瘤活性，在水中的溶解度高，因此可用作抗肿瘤剂。