2,6-anhydro-3,4,5-tri-O-benzyl-1,7-dideoxy-L-galacto-hept-1-enitol

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,6-anhydro-3,4,5-tri-O-benzyl-1,7-dideoxy-L-galacto-hept-1-enitol
• 英文别名: 2,6-anhydro-3,4,5-tri-O-benzyl-1-deoxy-L-fuco-hept-1-enitol；2,3,4-tri-O-benzyl-1-deoxy-1-methylidene-L-fucopyranose；1-methylidene-2,3,5-tri-O-benzyl-L-fucopyranoside；(2S,3R,4R,5S)-2-methyl-6-methylidene-3,4,5-tris(phenylmethoxy)oxane
• 化学式: C₂₈H₃₀O₄
• 分子量: 430.544
• InChiKey: HLDUEHJGBMOUMY-AXCRSINUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  32
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,6-anhydro-3,4,5-tri-O-benzyl-1,7-dideoxy-L-galacto-hept-1-enitol 在 偶氮二异丁腈 、 sodium methylate 作用下， 以 四氢呋喃 、 甲醇 、 苯 为溶剂， 反应 2.5h， 生成 1-S-methyl-2,6-anhydro-1,7-dideoxy-3,4,5-tri-O-benzyl-L-glycero-L-galacto-heptitol
  参考文献：
  名称：

  Studies on the synthesis of C-Glycoside sulfones as potential glycosyl transferase inhibitors

  摘要：

  beta-C-Glycoside sulfoxides and sulfones were prepared by radical addition of thiol acetic acid to exocyclic glycals followed by deacetylation, S-alkylation, and selective oxidation. These compounds are representative examples of a new class of molecules designed to be glycosyl transferase inhibitors. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(97)01021-1
• 作为产物：
  描述：

  2,3,4-tri-O-benzyl-α-L-fucopyranose 在 吡啶 、 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 1.5h， 生成 2,6-anhydro-3,4,5-tri-O-benzyl-1,7-dideoxy-L-galacto-hept-1-enitol
  参考文献：
  名称：

  Studies on the synthesis of C-Glycoside sulfones as potential glycosyl transferase inhibitors

  摘要：

  beta-C-Glycoside sulfoxides and sulfones were prepared by radical addition of thiol acetic acid to exocyclic glycals followed by deacetylation, S-alkylation, and selective oxidation. These compounds are representative examples of a new class of molecules designed to be glycosyl transferase inhibitors. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(97)01021-1

文献信息

• Highly (<i>Z</i>)-Diastereoselective Synthesis of Trifluoromethylated <i>exo</i>-Glycals via Photoredox and Copper Catalysis
  作者：Christophe J.-M. Frédéric、Jérôme Cornil、Mathilde Vandamme、Lidia Dumitrescu、Abdellatif Tikad、Raphaël Robiette、Stéphane P. Vincent

  DOI：10.1021/acs.orglett.8b02891

  日期：2018.11.2

  Highly (Z)-diastereoselective approaches for the synthesis of trifluoromethylated exo-glycals by copper and photoredox catalysis are described. These complementary reactions are applicable to a wide range of methylene exo-glycals generated from the corresponding pyranoses and furanoses and give trifluoromethylated compounds under mild conditions in moderate to good yields. DFT calculations have allowed

  高度（Ž）用于合成三氟甲基化的方法-diastereoselective外型由铜和photoredox催化-glycals中描述。这些互补反应适用于由相应的吡喃糖和呋喃糖酶产生的各种亚甲基外糖，并在温和的条件下以中等至良好的收率得到三氟甲基化的化合物。DFT计算已使观察到的（Z）-立体选择性合理化。
• <i>C</i>-Glycosyl Amino Acids through Hydroboration-Cross-Coupling of<i>exo</i>-Glycals and Their Application in Automated Solid-Phase Synthesis
  作者：Stefan Koch、Dieter Schollmeyer、Holger Löwe、Horst Kunz

  DOI：10.1002/chem.201300150

  日期：2013.5.27

  This makes glycopeptides an interesting class of compounds for medical applications. To enhance the long‐term availability of these molecules in vivo, the stabilization of the glycosidic bond between the amino acid residue and the carbohydrate is of interest. The described modular approach affords β‐linked C‐glycosyl amino acids by a sequence of Petasis olefination of glyconolactones, stereoselective

  O-糖基化是蛋白质翻译后最重要的修饰之一。碳水化合物对肽主链的附着会影响缀合物的构象以及溶解度，甚至对于在细胞间相互作用中与特定配体结合或在膜上进行主动转运而言，甚至是必不可少的。这使糖肽成为医学应用中有趣的一类化合物。为了提高这些分子在体内的长期可用性，关注氨基酸残基和碳水化合物之间糖苷键的稳定化。所描述的模块化方法提供了β-连接的C糖基氨基酸，包括糖基内酯的Petasis烯化反应，立体选择性硼氢化反应和轻度的B-烷基-Suzuki偶联反应。偶联产物被转化为适合固相合成的C-糖基氨基酸结构单元，并成功地掺入了与肿瘤相关的MUC1-糖肽的部分序列中。由此产生的C糖肽是O糖肽疫苗长期稳定模拟物开发的候选对象。
• Design and synthesis of a trisubstrate analogue for α(1→3)fucosyltransferase: A potential inhibitor
  作者：B.M. Heskamp、G.H. Veeneman、G.A.van der Marel、C.A.A. van Boeckel、J.H. van Boom

  DOI：10.1016/0040-4020(95)00451-d

  日期：1995.7

  Phenyl 1-azido-3,4,5-tri-O-benzyl-I-deoxy-2-seleno-α-l-fuco-heptulopyranoside (5), readily accessible from perbenzylated l-fucono-1,5-lactone, is a key intermediate in the preparation of trisubstrate analogue 2. NIS mediated condensation of fucosyl donor 5 with methyl 2,4,6-tri-O-benzyl-α-d-glucopyranoside (7) and ensuing reduction of the azido function furnished ketodisaccharide 10b, which was elongated

  苯基1-叠氮基3,4,5-三-O-苄基-I-脱氧-2-硒基-α-1-fuco-七吡喃吡喃糖苷（5），可从过苄基的1-fucono-1,5-内酯轻松获得，是制备三基质类似物2的关键中间体。NIS介导的岩藻糖基供体5与甲基2,4,6-三-O-苄基-α-d-吡喃葡萄糖苷（7）缩合，并随后降低了叠氮基官能团，提供了酮二糖10b，后者在1-氨基处被延长。带有丙二酸间隔基的岩藻糖残基。将如此获得的化合物脱保护，然后与5'-氨基-5'-脱氧-鸟苷偶联，得到目标化合物2。
• Petasis Olefination in a Continuous-Flow Microwave Reactor: exo-Glycals from Sugar Lactones
  作者：Horst Kunz、Stefan Koch、Holger Löwe

  DOI：10.1055/s-0030-1261163

  日期：2011.9

  An efficient Petasis olefination of sugar lactones under continuous-flow microwave conditions was developed. Their conversion into exo-glycals can be steered by adjusting the residence time and the concentration of the solution within the reactor. Applying a continuous-flow procedure, the reaction time can be shortened to less than three minutes, several hundred times shorter compared to values given in the literature for batch procedures. This setup is utilizable for a gram-scale synthesis of enol ethers and exo-glycals, in particular, such ones containing potentially (Lewis) acid sensitive acetalic protecting groups.

  在连续流动微波条件下，开发了糖内酯的高效Petasis烯化反应。通过调整反应器内溶液的停留时间和浓度，可以控制其转化为外向糖苷。采用连续流动工艺，反应时间可以缩短到3分钟以内，比文献中给出的间歇工艺值缩短了几百倍。这种装置可用于克级烯醇醚和外向糖苷的合成，特别是那些含有潜在（路易斯）酸敏感的乙缩醛保护基团的烯醇醚和外向糖苷。
• Studies on the synthesis of C-Glycoside sulfones as potential glycosyl transferase inhibitors
  作者：Jacquelyn Gervay、Terrence M. Flaherty、Daniel Holmes

  DOI：10.1016/s0040-4020(97)01021-1

  日期：1997.12

  beta-C-Glycoside sulfoxides and sulfones were prepared by radical addition of thiol acetic acid to exocyclic glycals followed by deacetylation, S-alkylation, and selective oxidation. These compounds are representative examples of a new class of molecules designed to be glycosyl transferase inhibitors. (C) 1997 Elsevier Science Ltd.