2,3,4,6-tetra-O-pivaloyl-D-galactopyranose

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2,3,4,6-tetra-O-pivaloyl-D-galactopyranose
• 英文别名: pivaloyl(-2)[pivaloyl(-3)][pivaloyl(-4)][pivaloyl(-6)]Gal；[(2R,3S,4S,5R)-3,4,5-tris(2,2-dimethylpropanoyloxy)-6-hydroxyoxan-2-yl]methyl 2,2-dimethylpropanoate
• 化学式: C₂₆H₄₄O₁₀
• 分子量: 516.629
• InChiKey: JYGDPQMHICAXOT-CHVQCXDUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  36
• 可旋转键数：
  13
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  135
• 氢给体数：
  1
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  2,3,4,6-tetra-O-pivaloyl-D-galactopyranose 在 吡啶 、 盐酸 作用下， 以 乙醇 、 水 为溶剂， 反应 32.0h， 生成 D-galactono-1,4-lactone
  参考文献：
  名称：

  稀有 l-糖内酯的简单通用合成

  摘要：

  开发了一种通过选择性反转 C-5 从 D-糖中合成稀有 L-糖内酯的简便方法。描述了羟胺对糖过新戊酸酯的选择性 1-脱酰。更实际的是，β-D-葡萄糖五乙酸酯可以通过这个简单的程序转化为 L-IDONO-1,4-内酯。

  DOI：

  10.1055/s-2007-977451
• 作为产物：
  描述：

  (2S)-N-(2,3,4,6-tetra-O-pivaloyl-β-D-galactopyranosyl)-2-(3-pyridyl)-5,6-didehydro-piperidin-4-one 在 盐酸 作用下， 以 甲醇 为溶剂， 生成 2,3,4,6-tetra-O-pivaloyl-D-galactopyranose
  参考文献：
  名称：

  Hetero-Diels-Alder reactions on a carbohydrate template: stereoselective synthesis of (S)-anabasin

  摘要：

  DOI：

  10.1021/jo00279a001

文献信息

• Carbohydrates as chiral templates: asymmetric ugi-synthesis of alpha-amino acids using galactosylamines as the chiral matrices
  作者：Horst Kunz、Waldemar Pfrengle

  DOI：10.1016/s0040-4020(01)86054-3

  日期：1988.1

  recrystallisation pure (R)-amino acid derivatives 5 are obtained in yields of 80–95%. In addition to the high yields and stereoselectivity the amino acid synthesis discribed here has the further advantage that it neither requires organometallic reagents and intermediates nor exclusion of oxygen and moisture. Two step acid hydrolysis of the N-galactosylamino acid amide derivatives 5 delivers the enantiomerically

  在路易斯酸催化剂存在下，O-乙酰基-（1）和O-新戊酰基-（2）保护的β-D-吡喃半乳糖胺与醛，异氰酸酯和羧酸在Ugi-四组分缩合反应生成相应的N-半乳糖基氨基酸酰胺衍生物3,5的定量收率基本相同。氯化锌是最有效的路易斯酸催化剂。在0℃或什至在室温下，氨基酸衍生物3，5的（2R，β-D）-非对映异构体以非对映高选择性形成。如果在-78°C至-25°C下使用空间要求更高的O-新戊酰半乳糖胺2，则立体选择性通常为20：1，有利于（2R，β-D）非对映异构体5。一次重结晶后，纯的（R）-氨基酸衍生物5的产率为80-95％。除了高产率和立体选择性之外，这里描述的氨基酸合成还具有以下优点：既不需要有机金属试剂和中间体，也不需要氧气和水分。N-半乳糖基氨基酸酰胺衍生物5的两步酸水解以高收率递送对映体纯的（R）-氨基酸8。
• High diastereoselective vinylogous Mannich reaction induced by O-pivaloylated d-galactosylamine as the chiral auxiliary: stereoselective synthesis of 8-arylazocan-2-one
  作者：Bing Cui、Gang Hou、Yan Cai、Zhiwei Miao

  DOI：10.1016/j.carres.2013.03.020

  日期：2013.6

  The diastereospecific formation of β-N-glycosidically linked α,β-unsaturated δ-amino aldehyde derivatives has been achieved with high yield via a vinylogous Mannich reaction. The reaction was performed by using a O-pivaloylated galactosyl amine as a chiral template and AlCl3 as a promoter in THF. (S)-8-(p-Nitrophenyl) azocan-2-one can be stereoselective synthesized from (S) ethyl 7-galactosylamino

  β-N-糖苷键连接的α，β-不饱和δ-氨基醛衍生物的非对映异构形成已通过乙烯基曼尼希反应以高收率实现。该反应通过在THF中使用O-聚乙烯醇化的半乳糖胺作为手性模板并且使用AlCl 3作为促进剂来进行。（S）-8-（对硝基苯基）偶氮烷-2-酮可通过双键的连续加氢反应从（S）7-半乳糖基氨基-7-（对硝基苯基）庚-2,4-二烯酸酯中立体合成，环内酰胺的形成，以及在碱性条件下去除N-糖苷助剂的过程。
• Lewis Acid Catalyzed Diastereoselective Vinylogous Mannich Reaction Induced by O-Pivaloylated d-Galactosylamine as the Chiral Auxiliary: Stereoselective Synthesis of 6-Arylpiperidin-2-ones
  作者：Zhiwei Miao、Ruyu Chen、Bing Cui、Shasha Kong、Guiping Wu

  DOI：10.1055/s-0031-1289635

  日期：2012.1

  derivatives, in the form of (S)-δ-amino-δ-arylpent-2-enoic ester, has been achieved in high yield via a vinylogous Mannich reaction, utilizing poly-O-pivaloylated d-galacosylamine as the chiral auxiliary. (S)-6-p-Tolylpiperidine-2-one can be stereoselectively synthesized from (S)-δ-amino-δ-arylpent-2-enoic ester by sequential hydrogenation of the double bond, cyclic lactam formation, and removal of

  （S）-δ-氨基-δ-芳基戊-2-烯酸酯形式的β-N-糖苷键连接的α，β-不饱和δ-氨基羰基衍生物的非对映特异性形成已通过乙烯基得到曼尼希反应，利用聚-O-聚乙烯醇化的d-半乳糖苷胺作为手性助剂。（S）-6-对甲苯基哌啶-2-酮可以通过（S）-δ-氨基-δ-芳基戊-2-烯酸酯通过顺序地双键加氢，环内酰胺的形成和除去的方式立体合成。在基本条件下为N-糖苷助剂。 乙烯基曼尼希反应-碳水化合物-手性助剂-立体选择性合成-6-芳基哌啶-2-酮
• Stereoselective Synthesis of α-Arylalkylamines by Glycosylation-induced Asymmetric Addition of Organometallic Compounds to Imines
  作者：Petra Allef、Horst Kunz

  DOI：10.1515/znb-2009-0609

  日期：2009.6.1

  Activation of imines of aromatic aldehydes by N-glycosylation with O-pivaloyl-galactopyranosyl bromide (pivalobromogalactose) and subsequent addition of organotin, organolithium, Grignard, or organozinc reagents afforded α-arylalkylamines with moderate to high diastereoselectivity. Graphical Abstract Stereoselective Synthesis of α-Arylalkylamines by Glycosylation-induced Asymmetric Addition of Organometallic

  通过用 O-新戊酰-吡喃半乳糖基溴（新戊溴半乳糖）进行 N-糖基化，然后加入有机锡、有机锂、格氏试剂或有机锌试剂，激活芳香醛的亚胺，得到具有中等至高非对映选择性的 α-芳基烷基胺。通过糖基化诱导的有机金属化合物与亚胺的不对称加成立体选择性合成α-芳基烷基胺
• Regioselective Glycosylation of Glucosamine and Galactosamine Derivates Using O-Pivaloyl Galactosyl Donors
  作者：Mathia Oßwald、Uwe Lang、Siglinde Friedrich-Bochnitschek、Waldemar Pfrengle、Horst Kunz

  DOI：10.1515/znb-2003-0808

  日期：2003.8.1

  Penta-O-pivaloyl-galactopyranose and tetra-O-pivaloyl-galactopyranosyl bromide after electrophilic activation reacted with 6-O-protected 2-azido-galactosides to give the precursor structures of the Thomsen-Friedenreich antigen disaccharide with high regioselectivity, but low yield.With 4,6-Obenzylidene protected 2-azidogalactosides and 2-O-pivaloyl phenylthio galactosides, T-antigen disaccharides of this type were obtained in good yields. Glycosylation reactions of 4,6-O-benzylidene protected glucosamine derivatives with O-pivaloyl protected galactosyl bromide efficiently gave lactolactosamine disaccharides. Even a thioglycoside was efficiently galactosylated by this method resulting in the formation of a disaccharide thioglycoside useful itself as a potential glycosyl donor.

  Penta-O-pivaloyl-galactopyranose和tetra-O-pivaloyl-galactopyranosyl溴在亲电活化后与6-O-保护的2-azido-galactosides反应，高选择性地形成Thomsen-Friedenreich抗原二糖的前体结构，但产率较低。使用4,6-Obenzylidene保护的2-azidogalactosides和2-O-pivaloyl苯硫基半乳苷，可以得到这种类型的T-抗原二糖，产率较高。4,6-O-benzylidene保护的葡萄糖氨基衍生物与O-pivaloyl保护的半乳苷溴的糖基化反应有效地产生了乳糖氨二糖。甚至通过这种方法，一种硫代糖苷也可以有效地被半乳苷化，形成一种作为潜在糖基供体的二糖硫代糖苷。