allyl 2,6-di-O-benzyl-α-D-galactopyranoside | 37111-91-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: allyl 2,6-di-O-benzyl-α-D-galactopyranoside
• 英文别名: (2R,3R,4S,5R,6S)-5-phenylmethoxy-2-(phenylmethoxymethyl)-6-prop-2-enoxyoxane-3,4-diol
• CAS: 37111-91-4
• 化学式: C₂₃H₂₈O₆
• 分子量: 400.472
• InChiKey: SAIBWTFYVQRZHJ-YSFPZDHXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  29
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  77.4
• 氢给体数：
  2
• 氢受体数：
  6

上下游信息

• 上游原料

  中文名称	英文名称	CAS号	化学式	分子量
  烯丙基-Α-D-吡喃半乳糖苷	(2S,3R,4S,5R,6R)-2-Allyloxy-6-hydroxymethyl-tetrahydro-pyran-3,4,5-triol	48149-72-0	C9H16O6	220.222
  ——	allyl 3,4-O-isopropylidene-α-D-galactopyranoside	81713-32-8	C12H20O6	260.287
  D-吡喃葡萄糖	D-Galactose	10257-28-0	C6H12O6	180.158

• 下游产品

  中文名称	英文名称	CAS号	化学式	分子量
  ——	allyl 2,6-di-O-benzyl-α-D-glucopyranoside	169822-03-1	C23H28O6	400.472
  ——	allyl 2,4,6-tri-O-benzyl-α-D-galactopyranoside	61236-87-1	C30H34O6	490.596
  ——	allyl 2,6-di-O-benzyl-3-O-(2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl)-α-D-galactopyranoside	282089-17-2	C57H62O11	923.113
  2,3,4,6-四-o-苄基-D-吡喃葡萄糖	2,3,4,6-tetra-O-benzyl-D-glucopyranose	6564-72-3	C34H36O6	540.656
  ——	2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl-(1->3)-2,4,6-tri-O-benzyl-α,β-D-galactopyranosyl fluoride	525585-41-5	C61H63FO10	975.164
  ——	3-O-α-D-galactopyranosyl-D-galactose	7313-98-6	C12H22O11	342.3

反应信息

• 作为反应物：
  描述：

  allyl 2,6-di-O-benzyl-α-D-galactopyranoside 在 三氟甲磺酸三甲基硅酯 、 4 A molecular sieve 、 4-甲基苯磺酸吡啶 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 3.67h， 生成 allyl O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-(1->3)-4-O-acetyl-2,6-di-O-benzyl-α-D-galactopyranoside
  参考文献：
  名称：

  Efficient and versatile synthesis of mucin-like glycoprotein mimics

  摘要：

  An efficient synthetic method of sequential glycopeptide-polymer by means of the combined chemical and enzymatic strategy was applied to the practical synthesis of some tandem repeating mucin-type glycoproteins. Versatility of the present synthetic strategy was demonstrated by elucidating some physicochemical and conformational analyses of these synthetic mucins. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(02)01359-5
• 作为产物：
  描述：

  Allyl 2,6-di-O-benzyl-3,4-O-isopropylidene-α-D-galactopyranoside 在 溶剂黄146 作用下， 以 水 为溶剂， 反应 2.0h， 生成 allyl 2,6-di-O-benzyl-α-D-galactopyranoside
  参考文献：
  名称：

  痢疾志贺氏菌3型的烯丙糖苷形式与O抗原重复单元相关的封闭五糖衍生物的合成

  摘要：

  从d-半乳糖胺盐酸盐，d-半乳糖和d-葡萄糖开始，四糖衍生物烯丙基2,3,6-三-O-苄基-4-O- [甲基（R）-2-丙酸酯]-β-d-吡喃葡萄糖基-（1→6）-2,3,4-三-O-苄基-α-d-吡喃葡萄糖基-（1→4）-2,6-二-O-苄基-3-O-（3,4已通过嵌段合成策略合成了6-6-三-O-乙酰基-2-脱氧-2-邻苯二甲酰亚胺基-β-d-吡喃半乳糖苷）-α-d-吡喃半乳糖苷，其中一个嵌段含有甲基（R）-2丙酸酯基。操纵该四糖衍生物的保护基，然后与半乳糖呋喃糖苷供体反应，得到所需的五糖衍生物，其形式为烯丙基糖苷，与痢疾志贺氏菌3型的再生成单元有关。

  DOI：

  10.1081/car-120023471

文献信息

• Synthesis of the Tetrasaccharide Repeating Unit from <i>Acinetobacter baumannii</i> Serogroup O18 Capitalizing on Phosphorus-Containing Leaving Groups
  作者：Ryoichi Arihara、Kosuke Kakita、Kazuhiro Yamada、Seiichi Nakamura、Shunichi Hashimoto

  DOI：10.1021/acs.joc.5b00139

  日期：2015.5.1

  The first convergent synthesis of the tetrasaccharide repeating unit of the polymeric O antigen isolated from Acinetobacter baumannii serogroup O18 has been achieved. The ManNAcβ1→4Gal and GalNAcβ1→3Gal units were successfully obtained through β-selective glycosylation with 2-azido-4,6-O-benzylidene-2-deoxymannosyl diphenyl phosphate and Tf2NH-promoted glycosylation with 2-acetamido-2-deoxygalactosyl

  从鲍曼不动杆菌血清群O18中分离出的聚合O抗原的四糖重复单元的第一次收敛合成已经完成。所述ManNAcβ1→4Gal和GalNAcβ1→与β3Gal单元被成功地通过β选择性糖基化得到2-叠氮基-4,6- ø -亚苄基-2- deoxymannosyl二苯基磷酸酯和TF 2与2-乙酰氨基-2- deoxygalactosyl NH-促进糖基化亚磷酸二乙酯分别。该二糖单元可以借助于作为磷酸二苯酯离去基团的活化剂的TMSC10 4偶联，并且整体脱保护完成了四糖的合成。
• “Standardized intermediates” for oligosaccharide synthesis. Precursors of d-galactopyranose residues having chain extension at position 3, or positions 3 and 2
  作者：Mina A. Nashed、Manjit S. Chowdhary、Laurens Anderson

  DOI：10.1016/s0008-6215(00)88053-2

  日期：1982.4

  -galactopyranosides 6a–d . These were converted into the glycosyl halides by published methods. An improved preparation of allyl 2,6-di- O -benzyl-( 15 ) and 2,4,6-tri- O -benzyl-( 19 ) α- d -galactopyranoside was achieved. The direct acetonation of 1 to the 3,4- O -isopropylidene derivative 13 , followed by benzylation and mild acid hydrolysis, gave 15 in 56% yield. The transient protection of O-3 in 15

  摘要一系列带有第二个苯甲酰基（8a，12a）或可选择性除去的临时保护基团（8b–d，2b）的2-O-苯甲酰基-4,6-二-O-苄基-α-d-吡喃半乳糖基卤化物。由烯丙基α-d-吡喃半乳糖苷（1）合成位置3处的12b）。关键中间体是1-丙烯基4,6-二-O-苄基-α-d-吡喃半乳糖苷（5），由1经4,6-O-亚苄基-2,3-二-O-巴豆基衍生物2制备。通过在低温下进行选择性酰化作用，依次引入2-O-苯甲酰基和各种3-取代基，得到完全取代的1-丙烯基α-d-吡喃半乳糖苷6a-d。通过公开的方法将它们转化为糖基卤化物。获得了改进的烯丙基2，6-二-O-苄基-（15）和2,4,6-三-O-苄基-（19）α-d-吡喃半乳糖苷的制备。将1直接乙酰化为3,4-O-异亚丙基衍生物13，然后进行苄基化和温和的酸水解，得到15，收率为56％。通过用（2-甲氧基乙氧基）甲基氯将二丁基亚锡衍生物16烷基化来完成1
• The Allyl Group for Protection in Carbohydrate Chemistry. XXXI. Conversion of Allyl 2,6-Di-O-benzyl-α-D-galactopyranoside Into Allyl 2,6-Di-O-benzyl-α-D-glucopyranoside and 2,6-Di-O-benzyl-D-glucopyranose
  作者：T Desai、J Gigg、R Gigg

  DOI：10.1071/ch9960305

  日期：——

  Allyl 2,6-di-O-benzyl-α-D-galactopyranoside was converted by tin-mediated alkylation into the 3-O-p-methoxybenzyl ether which gave the 4-O-mesyl derivative. Sodium benzoate in refluxing N,N-dimethylformamide converted the last compound into allyl 4-O-benzoyl-2,6-di-O-benzyl-3-O-p-methoxybenzyl-α-D-glucopyranoside in high yield. This was saponified and the product was treated with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone to give the required allyl 2,6-di-O-benzyl-α-D-glucopyranoside whose structure was confirmed by conversion into the known 2,3,4,6-tetra-O-benzyl-D-glucopyranose. Removal of the allyl group from allyl 2,6-di-O-benzyl-α-D-glucopyranoside by a standard procedure gave 2,6-di-O-benzyl-D-glucopyranose. Both of the title compounds are required as intermediates for the synthesis of analogues of the 'adenophostins'.

  烯丙基 2,6-二-O-苄基-α-D-吡喃半乳糖苷通过锡介导的烷基化反应转化为 3-O-对甲氧基苄基醚，从而得到 4-O-甲磺酰基衍生物。苯甲酸钠在回流的 N,N-二甲基甲酰胺中将最后一种化合物转化为 4-O-苯甲酰基-2,6-二-O-苄基-3-O-对甲氧基苄基-α-D-吡喃葡萄糖苷烯丙基，产量很高。将其皂化后，用 2,3-二氯-5,6-二氰基-1,4-苯醌处理产物，得到所需的烯丙基 2,6-二-O-苄基-α-D-吡喃葡萄糖苷，将其转化为已知的 2,3,4,6-四-O-苄基-D-吡喃葡萄糖，证实了其结构。通过标准程序从烯丙基 2,6-二-O-苄基-α-D-吡喃葡萄糖苷中去除烯丙基，得到 2,6-二-O-苄基-D-吡喃葡萄糖。这两种标题化合物都是合成 "腺苷 "类似物所需的中间体。
• A novel synthesis of α-d-Galp-(1→3)-β-d-Galp-1-O-(CH2)3NH2, its linkage to activated matrices and absorption of anti-αGal xenoantibodies by affinity columns
  作者：Jérôme Liaigre、Didier Dubreuil、Jean-Paul Pradère、Jean-François Bouhours

  DOI：10.1016/s0008-6215(00)00010-0

  日期：2000.5

  Pig organs transplanted into primates are rapidly rejected because of the interaction between Ga1 alpha(1-->3)Ga1 epitopes carried by the graft and natural antibodies (anti-alpha Ga1 antibodies) present in the blood of the recipient. This report describes a simplified synthesis of the xenogeneic disaccharide and its linkage to activated gel matrices. The digalactosides alpha-D-Ga1p-(1-->3)-alpha,beta-D-Ga1p-OAll were synthesized by the condensation of the trichloroacetimidoyl 2,3,4,6-tetra-O-benzyl-beta-D-galactopyranoside donor with the 3,4-unprotected allyl 2,6-di-O-benzyl-alpha- or beta-D-galactopyranoside acceptor precursor. Deallylation and hydrogenolysis led to the free digalactoside, whereas hydrogenolysis alone resulted in the 1-O-propyl digalactoside. Both products were tested by inhibition ELISA of natural anti-Ga1 alpha(1-->3)Ga1 antibodies. The alpha-D-Ga1p-(1-->3)-beta-D-Ga1p-OPr was found to be the best inhibitor. Thus, the allyl group of the partially benzylated alpha-D-Ga1p-(1-->3)-beta-D-Ga1p-OAll was engineered, via the hydroxy-, the tosyloxy- and the azidopropyl intermediates, into an aminopropyl group amenable to binding to N-hydroxysuccinimide-activated agarose gel matrices in order to obtain specific immunoabsorption columns. Columns made of gel substituted with 5 mu mol of disaccharide per milliliter were found efficient for the immunoabsorption of anti-alpha Ga1 antibodies from human plasma. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Synthesis of an intermediate fragment of the capsular polysaccharides of Klebsiella type 8
  作者：Da-Yan He、Zhan-Jiang Li、Meng-Shen Cai

  DOI：10.1016/0008-6215(93)84222-r

  日期：1993.2