methyl 2,3,4-tri-O-(phenylmethyl)-6-O-(3,4,6-tri-O-acetyl-2-deoxy-α-D-lyxohexopyranosyl)-α-D-glucopyranoside | 140186-46-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3,4-tri-O-(phenylmethyl)-6-O-(3,4,6-tri-O-acetyl-2-deoxy-α-D-lyxohexopyranosyl)-α-D-glucopyranoside
• 英文别名: Methyl 2,3,4-tri-O-benzyl-6-O-(3,4,6-tri-O-acetyl-2-deoxy-α-D-lyxo-hexopyranosyl)-α-D-glucopyranoside；methyl 6-O-(3,4,6-tri-O-acetyl-2-deoxy-α-D-lyxo-hexopyranosyl)-2,3,4-tri-O-benzyl-α-D-glucopyranoside；methyl 2,3,4-tri-O-benzyl-6-O-(3,4,6-tri-O-acetyl-2-deoxy-α-D-galactopyranosyl)-α-D-glucopyranoside；methyl 2,3,4-tri-O-benzyl-6-O-(3,4,6-tri-O-acetyl-2-deoxy-D-galactopyranosyl)-α-D-glucopyranoside；2-deoxy-D-lyxHex3Ac4Ac6Ac(a1-6)[Bn(-2)][Bn(-3)][Bn(-4)]a-Glc1Me；[(2R,3R,4R,6S)-3,4-diacetyloxy-6-[[(2R,3R,4S,5R,6S)-6-methoxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]methoxy]oxan-2-yl]methyl acetate
• CAS: 140186-46-5
• 化学式: C₄₀H₄₈O₁₃
• 分子量: 736.813
• InChiKey: NMKZZEPZZNADLE-YOLFTXTLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  53
• 可旋转键数：
  20
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  144
• 氢给体数：
  0
• 氢受体数：
  13

反应信息

• 作为产物：
  描述：

  1,3,4,6-tetra-O-acetyl-2-deoxy-2-iodo-α-D-talose 在 [Ir(mppy)₃] 、 N,N-二异丙基乙胺 、 4-甲苯硫酚 作用下， 以 甲苯 、 乙腈 为溶剂， 反应 0.33h， 生成 methyl 2,3,4-tri-O-(phenylmethyl)-6-O-(3,4,6-tri-O-acetyl-2-deoxy-α-D-lyxohexopyranosyl)-α-D-glucopyranoside
  参考文献：
  名称：

  可见光介导的还原脱碘作用实现α-连接的2-脱氧糖苷的立体选择性合成

  摘要：

  2-脱氧糖及其衍生物大量存在于许多重要的天然药物中。然而，具体的2-脱氧糖苷键的构建仍然是一个挑战。在此，我们报告了一种通过2-碘-糖基乙酸乙酸酯的糖基化和随后的可见光介导的无锡还原脱碘来制备2-脱氧-α-糖苷的有效方法。我们已成功地将糖基化后去碘化策略应用于30多种单糖，二糖，三糖，四糖和十五糖的合成，并具有出色的立体选择性和效率。该方法也已用于合成包含四个α-键的2-脱氧四糖。

  DOI：

  10.1002/chem.201405516

文献信息

• Copper Reactivity Can Be Tuned to Catalyze the Stereoselective Synthesis of 2-Deoxyglycosides from Glycals
  作者：Carlos Palo-Nieto、Abhijit Sau、Robin Jeanneret、Pierre-Adrien Payard、Aude Salamé、Maristela Braga Martins-Teixeira、Ivone Carvalho、Laurence Grimaud、M. Carmen Galan

  DOI：10.1021/acs.orglett.9b04525

  日期：2020.3.6

  We demonstrate that tuning the reactivity of Cu by the choice of oxidation state and counterion leads to the activation of both "armed" and "disarmed" type glycals toward direct glycosylation leading to the α-stereoselective synthesis of deoxyglycosides in good to excellent yields. Mechanistic studies show that CuI is essential for effective catalysis and stereocontrol and that the reaction proceeds

  我们证明，通过选择氧化态和抗衡离子来调节Cu的反应性会导致“武装”和“解除武装”型糖类朝着直接糖基化的活化，从而导致以良好的优良收率合成脱氧糖苷的α-立体选择性合成。机理研究表明，CuI对于有效催化和立体控制至关重要，并且该反应通过烯醇醚和OH亲核试剂的双重活化而进行。
• TMSBr-mediated solvent- and work-up-free synthesis of α-2-deoxyglycosides from glycals
  作者：Mei-Yuan Hsu、Yi-Pei Liu、Sarah Lam、Su-Ching Lin、Cheng-Chung Wang

  DOI：10.3762/bjoc.12.164

  日期：——

  The thio-additions of glycals were efficiently promoted by a stoichiometric amount of trimethylsilyl bromide (TMSBr) to produce S-2-deoxyglycosides under solvent-free conditions in good to excellent yields. In addition, with triphenylphosphine oxide as an additive, the TMSBr-mediated direct glycosylations of glycals with a large range of alcohols were highly α-selective.

  甘露糖醛酸盐的硫加成反应可以在无溶剂条件下高效地通过等物量的溴化三甲基硅(TMSBr)催化产生良好至优异收率的S-2-脱氧糖苷。此外，加入三苯基膦氧化物作为添加剂，TMSBr介导的甘露糖醛酸盐与多种醇类的直接糖基化反应具有高度α-选择性。
• Additive‐Free Gold(III)‐Catalyzed Stereoselective Synthesis of 2‐Deoxyglycosides Using Phenylpropiolate Glycosides as Donors
  作者：Mukta Shaw、Amit Kumar

  DOI：10.1002/asia.201900888

  日期：2019.12.13

  Stereoselective synthesis of deoxyglycosides has been achieved from benchtop stable and easily synthesizable deoxy-phenylpropiolate glycosides (D-PPGs) using gold(III) salt as catalyst under external additive-free conditions. Under a simple catalytic system, D-PPGs reacted with a variety of sugar and non-sugar acceptors to produce majorly α-stereoselective O/N-deoxyglycosides in good to excellent yields

  在无外部添加剂的条件下，使用金（III）盐作为催化剂，可从台式稳定且易于合成的脱氧苯丙酸丙二醇酯（D-PPGs）中实现脱氧糖苷的立体选择性合成。在简单的催化系统下，D-PPG与多种糖和非糖受体反应，以高至优异的收率产生主要的α-立体选择性O / N-脱氧糖苷，并再生易于分离和重用的苯丙酸。在优化的反应条件下，含有武装和解除武装团体的脱氧PPG能够很好地存活。另外，展示了D-PPG的正交性质，并且还合成了1，1'-连接的海藻糖型糖。
• Stereoselective Synthesis of 2‐Deoxyglycosides from Glycals by Visible‐Light‐Induced Photoacid Catalysis
  作者：Gaoyuan Zhao、Ting Wang

  DOI：10.1002/anie.201800909

  日期：2018.5.22

  The direct, photoacid‐catalyzed synthesis of 2‐deoxyglycosides from glycals is reported. A series of phenol‐conjugated acridinium‐based organic photoacids were rationally designed, synthesized, and studied alongside the commercially available phenolic catalyst eosin Y. In the presence of such a photoacid catalyst and light, synthetic glycals were activated and coupled with a range of alcohols to afford

  据报道，由糖类直接，光酸催化合成了2-脱氧糖苷。与市售的酚催化剂曙红Y一起，合理设计，合成和研究了一系列基于酚共轭啶基的有机光酸。在这种光酸催化剂和光的存在下，合成糖被活化并与多种醇偶联以高收率和优异的α-选择性提供2-脱氧糖苷。
• Bismuth-Catalyzed Stereoselective 2-Deoxyglycosylation of Disarmed/Armed Glycal Donors
  作者：Manoj Kumar、Aakanksha Gurawa、Nitin Kumar、Sudhir Kashyap

  DOI：10.1021/acs.orglett.1c04008

  日期：2022.1.21

  Bi(OTf)3 promoted direct and highly stereoselective glycosylation of “disarmed” and “armed” glycals to synthesize 2-deoxyglycosides has been reported. The tunable and solvent-controlled chemoselective activation of deactivated glycal donors distinguishing the competitive Ferrier and 1,2-addition pathways was discovered to improve substrate scope. The practical versatility of the method has been amply

  据报道，Bi(OTf) 3促进“解除武装”和“武装”糖苷的直接和高度立体选择性糖基化以合成 2-脱氧糖苷。发现可调谐和溶剂控制的化学选择性激活失活的糖供体区分竞争性 Ferrier 和 1,2-加成途径，以改善底物范围。该方法的实用多功能性已通过高价值天然产物和药物的寡糖合成和 2-脱氧糖基化得到充分证明。