2,3,4,6-tetra-O-benzyl-D-mannono-1,5-lactone | 82598-88-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3,4,6-tetra-O-benzyl-D-mannono-1,5-lactone
• 英文别名: 2,3,4,6-tetra-O-benzyl-D-manno-1,5-lactone；2,3,4,6-tetra-O-benzyl-D-mannolactone；2,3,4,6-tetra-O-benzyl-D-mannonolactone；2,3,4,6-tetra-O-benzyl-D-mannono-δ-lactone；(3S,4S,5R,6R)-3,4,5-tribenzyloxy-6-(benzyloxymethyl)tetrahydropyran-2-one；(3S,4S,5R,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-one
• CAS: 82598-88-7
• 化学式: C₃₄H₃₄O₆
• 分子量: 538.64
• InChiKey: BUBVLQDEIIUIQG-FYZVQMPESA-N

物化性质

• 沸点：
  677.7±55.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  40
• 可旋转键数：
  13
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,3,4,6-tetra-O-benzyl-D-mannono-1,5-lactone 在 三乙基硅烷 、 正丁基锂 、 三氟甲磺酸三甲基硅酯 、 4 A molecular sieve 作用下， 以 二氯甲烷 为溶剂， 反应 2.66h， 生成 2-(2,3,4,6-Tetra-O-benzyl-β-D-mannopyranosyl)thiazole
  参考文献：
  名称：

  Thiazole-Based Synthesis of Formyl C-Glycosides

  摘要：

  A method for the installation of the formyl group at the anomeric position of pyranoses and furanoses starting from the corresponding lactones has been developed. The strategy involves the addition of 2-lithiothiazole to the sugar lactone, followed by the silane reduction of the acetylated resultant ketol and the unmasking of the formyl group from the thiazole ring. All steps have been studied in some details to improve chemical efficiency and stereochemical control. Hence, reversed alpha:beta ratios of ketols were found in kinetic and thermodynamic mixtures, the former being consistent with a steric effect control of the substituents and the latter by the electronic effect of the ring oxygen. Seven sugar aldehydes with different D-pyranosidic (2,3,4,6-tetra-O-benzyl-gluco, -galacto, and -manno, 2-azido-3,4,6-tri-O-benzyl-2-deoxy-galacto) and D-furanosidic moieties (5-O-benzyl-2,3-isopropylidene-ribo; 2,3,5-tri-O-benzyl-ribo; 2,3:5,6-di-O-isopropylidene-manno) were prepared in 52-65% isolated overall yield from the corresponding lactone.

  DOI：

  10.1021/jo00100a050
• 作为产物：
  描述：

  phenacyl 2,3,4,6-tetra-O-benzyl-α-D-mannopyranoside 以 苯 为溶剂， 反应 24.0h， 以90%的产率得到2,3,4,6-tetra-O-benzyl-D-mannono-1,5-lactone
  参考文献：
  名称：

  分子内氢原子提取：Norrish II型光反应中的β-氧效应

  摘要：

  描述了α-和β-四苄基吡喃葡萄糖，α-四苄基甘露吡喃糖和2-羟基四氢吡喃的苯甲酰基糖苷的制备。每种化合物通过派热克斯（Pyrex）的光解均能通过Norrish II型光解清楚地形成内酯。描述了竞争实验，其证明了在光解过程中两种葡糖基异构体以相同的速率消耗。相似的实验确定，苯甲酰基α-葡萄糖苷比相应的α-甘露糖苷具有更高的反应性。四氢吡喃衍生物被碳水化合物裂解得更快。用碳水化合物系列中的β-氧键使氢原子提取的极化转变陈旧性失去稳定作用，可以解释这种作用。

  DOI：

  10.1016/0040-4020(95)00755-w

文献信息

• Highly Stereoselective Nucleophilic Addition of Difluoromethyl-2-pyridyl Sulfone to Sugar Lactones and Efficient Synthesis of Fluorinated 2-Ketoses
  作者：Xiao Liu、Qiang Yin、Jian Yin、Guohua Chen、Xin Wang、Qi-Dong You、Yue-Lei Chen、Bing Xiong、Jingkang Shen

  DOI：10.1002/ejoc.201402757

  日期：2014.10

  sulfone to sugar lactones proceeded with good yield and excellent stereoselectivity. The hitherto unknown direct addition intermediates are stable and capable of useful conversions: Formal elimination of the anomeric hydroxy and sulfonyl groups yielded a 1-deoxy-1-difluoromethylene mannopyranose derivative. Directly from sugar lactones, by nucleophilic addition and subsequent one-pot reduction with

  二氟甲基-2-吡啶基砜与糖内酯的亲核加成具有良好的收率和优异的立体选择性。迄今为止未知的直接加成中间体是稳定的并且能够进行有用的转化：异头羟基和磺酰基的形式消除产生1-脱氧-1-二氟亚甲基吡喃甘露糖衍生物。直接从糖内酯中，通过亲核加成和随后的烯丙基氯化镁一锅还原，有效地制备了前所未有的氟化 2-酮糖类似物。
• Synthesis of C-spiro-glycoconjugates from sugar lactones via zinc mediated Barbier reaction
  作者：Mallikharjuna Rao Lambu、Altaf Hussain、Deepak K. Sharma、Syed Khalid Yousuf、Baldev Singh、Anil. K. Tripathi、Debaraj Mukherjee

  DOI：10.1039/c3ra46796a

  日期：——

  Anomeric gem-diallylation, mono-β-crotylation and mono-β-propargylation of sugar 1,5 and 1,4 lactones have been achieved under Barbier reaction conditions using Zn powder and a catalytic amount of TMSCl as an activator. Ring closing olefin metathesis of the synthesized gem-diallyl derivatives furnished C-spiro cyclopentene glycosides. Finally, the cyclopentene rings were converted into carbohydrate based tricyclic morpholine fused triazole glycoconjugates as potential SGLT2 inhibitors.

  使用Zn粉和催化量的TMSCl作为活化剂，在Barbier反应条件下实现了糖1,5和1,4内酯的anomeric双二烯基化、单-β-罗汀基化和单-β-丙炔基化。合成的双二烯基衍生物经过环闭合烯烃复分解反应得到C-螺环戊烯糖苷。最后，将环戊烯环转化为基于碳水化合物的三环吗啉并三唑糖缀合物，作为潜在的SGLT2抑制剂。
• 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。
• Novel synthesis of oligosaccharides linked with carbamate and urea bonds utilizing modified Curtius rearrangement
  作者：Daisuke Sawada、Shinya Sasayama、Hideyo Takahashi、Shiro Ikegami

  DOI：10.1016/j.tet.2008.06.089

  日期：2008.9

  describe a novel synthesis of various carbamate- and urea-linked disaccharides stereospecifically using sugar carboxylic acids and sugar alcohols or sugar amines by the modified Curtius rearrangement. In this reaction, the reactivity of each hydroxyl group in glucose as an acceptor has been disclosed. Furthermore, we applied this method to the synthesis of carbamate-linked oligosaccharides including

  我们描述了一种新型合成的各种氨基甲酸酯和脲连接的二糖，使用糖羧酸和糖醇或糖胺，经修饰的库尔修斯重排立体定向。在该反应中，已经公开了葡萄糖中每个羟基作为受体的反应性。此外，我们将此方法应用于包括树突状分子的氨基甲酸酯连接的寡糖的合成。
• Iodine Monochloride (ICl) as a Highly Efficient, Green Oxidant for the Oxidation of Alcohols to Corresponding Carbonyl Compounds
  作者：Peng Wei、Datong Zhang、Zhigang Gao、Wenqing Cai、Weiren Xu、Lida Tang、Guilong Zhao

  DOI：10.1080/00397911.2015.1005630

  日期：2015.6.18

  ABSTRACT Iodine monochloride (ICl) was discovered to be a highly efficient, green oxidant, which can oxidize aldose hemiacetals, diarylmethanols, arylalkylmethanols, anddialkylmethanols to the corresponding aldose lactones, diarylmethanones, arylalkylmethanones, and dialkylmethanones, respectively, in high yields. ICl as a green, metal-free oxidant is characterized by mild reaction condition, short reaction

  摘要 一氯化碘 (ICl) 被发现是一种高效的绿色氧化剂，可以将醛糖半缩醛、二芳基甲醇、芳烷基甲醇和二烷基甲醇分别以高产率氧化成相应的醛糖内酯、二芳基甲酮、芳基烷基甲酮和二烷基甲酮。ICl作为一种绿色无金属氧化剂，具有反应条件温和、反应时间短、收率好、适用范围广等特点。图形概要