((2S,3R,4S,5S,6R)-3,4,5-Tris-benzyloxy-6-benzyloxymethyl-2-hydroxy-tetrahydro-pyran-2-yl)-acetic acid tert-butyl ester | 400888-39-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ((2S,3R,4S,5S,6R)-3,4,5-Tris-benzyloxy-6-benzyloxymethyl-2-hydroxy-tetrahydro-pyran-2-yl)-acetic acid tert-butyl ester
• 英文别名: tert-butyl 2-[(2S,3R,4S,5S,6R)-2-hydroxy-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl]acetate
• CAS: 400888-39-3
• 化学式: C₄₀H₄₆O₈
• 分子量: 654.8
• InChiKey: XQASVMWAABDLDE-WHBOPOCKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  48
• 可旋转键数：
  17
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  92.7
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  ((2S,3R,4S,5S,6R)-3,4,5-Tris-benzyloxy-6-benzyloxymethyl-2-hydroxy-tetrahydro-pyran-2-yl)-acetic acid tert-butyl ester 在 palladium dihydroxide 三氟化硼乙醚 、 氢气 、 caesium carbonate 、 三氟乙酸 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 5.0h， 生成 ((3R,4S,5R,6R)-3,4,5-Trihydroxy-6-hydroxymethyl-2-methoxy-tetrahydro-pyran-2-yl)-acetic acid methyl ester
  参考文献：
  名称：

  Synthesis of Sugar-fused GABA-analogs

  摘要：

  γ-氨基丁酸（GABA）-糖类类似物以C-酮苷的形式可以从d-或l-葡萄糖内酯和d-半乳糖内酯出发，通过4到7个步骤合成。合成的关键步骤是以三甲基氟甲基磺酸酯（TMS-OTf）促进的2-脱氧-3-呋喃糖酸与三甲基氰化物的C-糖苷化反应。通过氢化得到的β-氰酯可以提供GABA类似物，这些类似物是在糖骨架上表现的。

  DOI：

  10.1055/s-2001-18097
• 作为产物：
  描述：

  2,3,4,6-四-O-苄基-D-吡喃半乳糖 在 molecular sieve 、 magnesium 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 ((2S,3R,4S,5S,6R)-3,4,5-Tris-benzyloxy-6-benzyloxymethyl-2-hydroxy-tetrahydro-pyran-2-yl)-acetic acid tert-butyl ester
  参考文献：
  名称：

  A new Co(0) complex mediated synthesis of C-glycoside analogues

  摘要：

  Properly protected glyconolactones, readily available from the parent sugars, react under mild conditions with alpha-bromoacetates in the presence of a soluble Co(0) complex, either in stoichiometric Or substoichiometric amounts, to give a Reformatsky-type addition product to the lactone. The addition product can be Subsequently converted into a variety of compounds: dehydroxylation with triethylsilane in the presence of boron trifluoride affords C-glycosides. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(03)00533-0

文献信息

• Alkylation Reactions Using a Galactose-Based β-Keto Ester Enolate and Conversion into β-<i>C</i>-Galactosides
  作者：Frank Schweizer、Dhananjoy Mondal

  DOI：10.1055/s-2008-1078176

  日期：——

  A de novo approach for the synthesis of biologically important C-galactosides has been achieved via use of an acyclic galactose-derived β-keto ester. The β-keto ester enolate serves as a C-nucleophile and reacts with primary alkyl halides and Michael acceptors to generate alkylation products that can be converted into β-C-galactosides and C-disaccharide mimics with high stereoselectivity.

  已经通过使用无环半乳糖衍生的 β-酮酯实现了一种从头合成具有生物学意义的 C-半乳糖苷的方法。β-酮酯烯醇化物作为 C-亲核试剂，与伯烷基卤化物和迈克尔受体反应生成烷基化产物，该产物可转化为具有高立体选择性的 β-C-半乳糖苷和 C-二糖模拟物。
• Ritter-based glycoconjugation of amino acids and peptides—access to novel glycoconjugates displaying a β-amide linkage between amino acid and sugar moiety
  作者：Marlin Penner、Frank Schweizer

  DOI：10.1016/j.carres.2006.11.006

  日期：2007.1

  Beta-peptidic-D-gluco-, D-galacto-, and L-fuco-configured glycosyl amino acids can be prepared from the corresponding 2-deoxy-oct-3-ulopyranosonic acids via a one-pot intramolecular Ritter reaction. Initially, a ketopyranoside-based acid condenses under Lewis acid promoted conditions with nitriles (PhCN, MeCN) and a partially protected diamino ester (Boc-DAB-O-t-Bu, Boc-Orn-O-t-Bu) to form a beta-peptidic

  β-肽-D-葡萄糖-，D-半乳糖和L-fuco-构型的糖基氨基酸可以通过一锅内分子Ritter反应由相应的2-deoxy-oct-3-ulopyranosonic酸制备。最初，基于酮吡喃糖苷的酸在路易斯酸促进的条件下与腈（PhCN，MeCN）和部分受保护的二氨基酯（Boc-DAB-Ot-Bu，Boc-Orn-Ot-Bu）缩合形成β-肽糖基氨基叔丁基酯。糖基氨基叔丁基酯可以被转化为Fmoc保护的糖基氨基酸，其被适当地保护用于固相糖肽合成。此外，用固定的肽胺代替被保护的二氨基酯允许在固相上肽的合成后的N-末端和N（ε）-糖缀合。
• Synthesis of a galacto-configured C-ketoside-based γ-sugar-amino acid and its use in peptide coupling reactions
  作者：Frank Schweizer、Ole Hindsgaul

  DOI：10.1016/j.carres.2006.03.006

  日期：2006.7

  gamma-Sugar-amino acid analogues in the form of C-ketosides can be prepared in 5-6 steps starting from D-galactono-1,5-lactone. The key step in the synthesis is the trimethylsilyl trifluoromethanesulfonate (TMSOTf) promoted C-glycosylation of 2-deoxy-3-ulopyranosonates with trimethylsilyl cyanide. Hydrogenation of the resulting beta-cyano esters provides C-ketoside-based gamma-sugar-amino acids that serve as building blocks for the synthesis of unnatural neoglycopeptides. (c) 2006 Elsevier Ltd. All rights reserved.
• Synthesis of Sugar-fused GABA-analogs
  作者：Frank Schweizer、Albin Otter、Ole Hindsgaul

  DOI：10.1055/s-2001-18097

  日期：——

  γ-Aminobutyric acid (GABA)-sugar analogs in the form of C-ketosides can be prepared in 4 to 7 steps starting from d- or l-Glucono- and d-Galactono-1,5-lactone. The key step in the synthesis is the trimethylsilyl-trifluoromethanesulfonate (TMS-OTf) promoted C-glycosylation of 2-deoxy-3-ulopyranosonates with trimethylsilyl cyanide. Hydrogenation of the resulting β-cyano esters provides GABA-analogs, which are presented on a sugar scaffold.

  γ-氨基丁酸（GABA）-糖类类似物以C-酮苷的形式可以从d-或l-葡萄糖内酯和d-半乳糖内酯出发，通过4到7个步骤合成。合成的关键步骤是以三甲基氟甲基磺酸酯（TMS-OTf）促进的2-脱氧-3-呋喃糖酸与三甲基氰化物的C-糖苷化反应。通过氢化得到的β-氰酯可以提供GABA类似物，这些类似物是在糖骨架上表现的。
• A new Co(0) complex mediated synthesis of C-glycoside analogues
  作者：Fulvia Orsini、Emanuela Di Teodoro

  DOI：10.1016/s0957-4166(03)00533-0

  日期：2003.9

  Properly protected glyconolactones, readily available from the parent sugars, react under mild conditions with alpha-bromoacetates in the presence of a soluble Co(0) complex, either in stoichiometric Or substoichiometric amounts, to give a Reformatsky-type addition product to the lactone. The addition product can be Subsequently converted into a variety of compounds: dehydroxylation with triethylsilane in the presence of boron trifluoride affords C-glycosides. (C) 2003 Elsevier Ltd. All rights reserved.