methyl 3-deoxy-3-fluoro-β-D-xylopyranoside | 14536-99-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: methyl 3-deoxy-3-fluoro-β-D-xylopyranoside
• 英文别名: (2R,3S,4S,5R)-4-fluoro-2-methoxyoxane-3,5-diol
• CAS: 14536-99-3
• 化学式: C₆H₁₁FO₄
• 分子量: 166.149
• InChiKey: GSEFPHDIHMGBBC-JGWLITMVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 3-deoxy-3-fluoro-β-D-xylopyranoside 在 吡啶 、 盐酸 、 碘 、 potassium carbonate 作用下， 以 1,4-二氧六环 、 甲醇 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 45.0h， 生成 N-benzyl-3-fluoro-2,4-imino-2,3,4-trideoxy-L-ribonic acid
  参考文献：
  名称：

  3-Fluoroazetidinecarboxylic Acids and trans,trans-3,4-Difluoroproline as Peptide Scaffolds: Inhibition of Pancreatic Cancer Cell Growth by a Fluoroazetidine Iminosugar

  摘要：

  Reverse aldol opening tenders amides of 3-hydroxyazetidinecarboxylic acids (3-OH-Aze) unstable above pH 8. Axe, found in sugar beet, is mis-incorporated for proline in peptides in humans and is associated with multiple sclerosis and teratogenesis. Axe-containing peptides may be oxygenated by prolyl hydroxylases resulting in potential damage of the protein by a reverse aldol of the hydroxyazetidine; this, rather than changes in conformation; may account for the deleterious effects of Axe. This paper describes the synthesis of 3-fluoro-Aze amino acids as hydroxy-Aze analogues which are not susceptible to aldol cleavage. 4-(Azidomethyl)-3-fluoro-Aze and 3,4-difluoroproline are new peptide building blocks. trans,trans-2,4-dihydroxy-3-fluoroazetidine, an iminosugar, inhibits the growth of pancreatic cancer cells to a similar degree as gemcitabine.

  DOI：

  10.1021/acs.joc.5b00463
• 作为产物：
  描述：

  甲基 2,3-脱水-beta-D-核吡喃糖苷 在 potassium hydrogen bifluoride 作用下， 以 正庚烷 为溶剂， 反应 5.0h， 以70%的产率得到methyl 3-deoxy-3-fluoro-β-D-xylopyranoside
  参考文献：
  名称：

  通过环氧化物的开环氟化反应选择性地将氟原子引入碳水化合物和核苷中

  摘要：

  使用四丁基氟化氢铵（TBABF）-KHF 2或Et 3 N-3HF在微波辐射下进行环氧化物的开环氟化反应，以将氟原子引入碳水化合物分子中。当TBABF-KHF 2用作氟化试剂时，氟原子被区域选择性地引入，并且各种官能团可以耐受该条件。当在微波辐射下使用Et 3 N-3HF时，与传统的油浴加热相比，反应时间可以大大缩短。

  DOI：

  10.1016/j.jfluchem.2006.04.001

文献信息

• Positional specificity of Flavobacterium johnsoniae acetylxylan esterase and acetyl group migration on xylan main chain
  作者：Vladimír Puchart、Morten Gjermansen、Mária Mastihubová、Kristian B.R. Mørkeberg Krogh、Peter Biely

  DOI：10.1016/j.carbpol.2019.115783

  日期：2020.3

  are attacked with a significantly reduced affinity. The resulting 2-O-acetylated xylan was used to investigate for the first time the migration of the 2-O-acetyl group to position 3 within the polysaccharide. In contrast to easy acetyl group migration along the monomeric xylopyranosides or non-reducing-end terminal Xylp residues of xylooligosaccharides, such a migration in the polymer required much longer

  一种新的约翰逊弗氏菌分离物编码的酶与最近发现的新型乙酰木聚糖酯酶基本相同，该酶能够从4-O-甲基-d-葡萄糖醛酸取代的吡喃吡喃糖基（Xylp）残基中释放3-O-乙酰基（Razeq等等人，2018年）。除了乙酰葡糖醛酸木聚糖中2-O-MeGlcA取代的Xylp残基的去酯化作用外，该酶还对双乙酰化的Xylp残基同样起作用，从中仅释放3-O-乙酰基，而2-O-乙酰基则保持不变。3-O-单乙酰基化的木糖残基以显着降低的亲和力被攻击。所得的2-O-乙酰化木聚糖首次用于研究2-O-乙酰基向多糖内第3位的迁移。与容易的乙酰基沿着木糖寡糖的单体木糖吡喃糖苷或非还原末端Xylp残基迁移相比，这种在聚合物中的迁移需要在100°C下加热更长的时间。然而，木聚糖3-O-脱乙酰基酶的特异性对乙酰化的甲基和4-硝基苯基木吡喃葡萄糖苷没有那么严格的要求。
• Deoxy and deoxyfluoro analogues of acetylated methyl β-d-xylopyranoside––substrates for acetylxylan esterases
  作者：Mária Mastihubová、Peter Biely

  DOI：10.1016/j.carres.2004.06.001

  日期：2004.8

  synthesized via 2,3-anhydropentopyranoside precursors. Methyl 2,3-anhydro-4-O-benzyl-beta-D-ribopyranoside was transformed into methyl 2,3-anhydro-4-O-benzyl-beta-D-lyxopyranoside in three steps. The epoxide ring opening of 2,3-anhydropentopyranosides was accomplished either by hydride reduction or hydrofluorination. Methyl beta-D-xylopyranoside 2,3,4-tri-O-, 2,4-di-O-, and 3,4-di-O-acetates, and the prepared

  通过2,3合成了乙酰氧基木聚糖酯酶，二-O-乙酰化甲基β-D-吡喃吡喃糖苷的2-脱氧，3-脱氧，2-脱氧-2-氟和3-脱氧-3-氟衍生物的四种修饰底物-脱水戊吡喃糖苷前体。通过三个步骤将甲基2,3-脱水-4-O-苄基-β-D-核吡喃糖苷转化为甲基2,3-脱水-4-O-苄基-β-D-核吡喃糖苷。通过氢化物还原或氢氟化来完成2，3-脱水戊基吡喃糖苷的环氧开环。测试了β-D-吡喃吡喃二甲基2,3,4-tri-O-，2,4-di-O-和3,4-di-O-乙酸酯和制备的二乙酸酯类似物作为乙酰木聚糖酯酶底物的来源裂褶菌公社和里氏木霉。其脱乙酰基速率的测量指出了底物酶的独特结构要求。
• Fluorocarbohydrates
  作者：J.A. Wright、N.F. Taylor

  DOI：10.1016/s0008-6215(00)82209-0

  日期：1967.1

  potassium hydrogen fluoride (KHF 2 ) in ethane-1,2-diol on methyl 2,3-anhydro-4- O -benzyl-β- D -ribopyranoside ( 1 ) and methyl 2,3-anhydro-5- O -benzyl-α- D -lyxofuranoside ( 7 ) has been examined. In both cases the expected trans scission of the epoxide ring occurs to yield methyl 4- O -benzyl-3-deoxy-3-fluoro-β- D -xylopyranoside ( 2 ) and methyl 5- O -benzyl-3-deoxy-3-fluoro-α- D -arabinofuranoside

  摘要乙烷-1,2-二醇中的氟化氢钾（KHF 2）对甲基2,3-脱水-4-O-苄基-β-D-核吡喃糖苷（1）和甲基2,3-脱水-5的作用已经检查了-O-苄基-α-D-呋喃呋喃糖苷（7）。在这两种情况下，发生环氧化物环的预期反式断裂以产生甲基4-O-苄基-3-脱氧-3-氟-β-D-吡喃吡喃糖苷（2）和甲基5-O-苄基-3-脱氧-3 -氟-α-D-阿拉伯呋喃糖苷（8）。通过催化氢化建立了化合物（2）的结构，该催化氢化除去了苄基，得到不消耗高碘酸盐的结晶糖苷（3）。甲基3-脱氧-3-氟-β-D-吡喃吡喃糖苷（3）的酸水解产生了浆状的3-脱氧-3-氟-αβ-D-木糖浆（5），其特征在于为2,5-二氯苯基hydr糖浆。化合物（8）的酸水解产生了还原糖（9），其特征在于为苯hydr。化合物（9）消耗1mol。的高碘酸盐和释放的甲酸与结构5-O-苄基-3-脱氧-3-氟-αβ-D-阿拉伯糖一致。氟代醇（8）
• A common access to 2- and 3-substituted methyl β-d-xylopyranosides
  作者：Mária Mastihubová、Peter Biely

  DOI：10.1016/s0040-4039(01)01957-8

  日期：2001.12

  2-Deoxy-, 3-deoxy-, 2-deoxy-2-fluoro- and 3-deoxy-3-fluoro- derivatives of methyl beta -D-xylopyranoside diacetates were prepared by a new common route via 2,3-anhydropentosides. The stereo- and regioselective introduction of fluorine or hydrogen was accomplished by epoxide ring opening of methyl 2,3-anhydro-beta -D-ribopyranoside and methyl 2,3-anhydro-4-O-benzyl-beta -D-lyxopyranoside. Methyl 2.3-anhydro-4-O-benzyl-beta -D-lyxopyranoside was originally obtained in three simple steps from readily available methyl 2,3-anhydro-4-O-benzyl-beta -D-ribopyrinoside. (C) 2001 Elsevier Science Ltd. All rights reserved.
• 3-Fluoroazetidinecarboxylic Acids and <i>trans,trans-</i>3,4-Difluoroproline as Peptide Scaffolds: Inhibition of Pancreatic Cancer Cell Growth by a Fluoroazetidine Iminosugar
  作者：Zilei Liu、Sarah F. Jenkinson、Tom Vermaas、Isao Adachi、Mark R. Wormald、Yukako Hata、Yukiko Kurashima、Akira Kaji、Chu-Yi Yu、Atsushi Kato、George W. J. Fleet

  DOI：10.1021/acs.joc.5b00463

  日期：2015.5.1

  Reverse aldol opening tenders amides of 3-hydroxyazetidinecarboxylic acids (3-OH-Aze) unstable above pH 8. Axe, found in sugar beet, is mis-incorporated for proline in peptides in humans and is associated with multiple sclerosis and teratogenesis. Axe-containing peptides may be oxygenated by prolyl hydroxylases resulting in potential damage of the protein by a reverse aldol of the hydroxyazetidine; this, rather than changes in conformation; may account for the deleterious effects of Axe. This paper describes the synthesis of 3-fluoro-Aze amino acids as hydroxy-Aze analogues which are not susceptible to aldol cleavage. 4-(Azidomethyl)-3-fluoro-Aze and 3,4-difluoroproline are new peptide building blocks. trans,trans-2,4-dihydroxy-3-fluoroazetidine, an iminosugar, inhibits the growth of pancreatic cancer cells to a similar degree as gemcitabine.