1,2:4,5-di-O-isopropylidene-3-amino-3-deoxy-β-D-fructopyranose | 402856-06-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: 1,2:4,5-di-O-isopropylidene-3-amino-3-deoxy-β-D-fructopyranose
• CAS: 402856-06-8
• 化学式: C₁₂H₂₁NO₅
• 分子量: 259.302
• InChiKey: WXKFHWPBLJNKJV-XBWDGYHZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.34
• 重原子数：
  18.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  72.17
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  1,2:4,5-di-O-isopropylidene-3-amino-3-deoxy-β-D-fructopyranose 在 hexokinase 盐酸 、 5’-三磷酸腺苷 、 柠檬酸 、 magnesium chloride 作用下， 以 水 为溶剂， 反应 24.0h， 生成 3-amino-3-deoxy-D-fructose 6-phosphate
  参考文献：
  名称：

  Biosynthesis of 1-Deoxy-1-imino-d-erythrose 4-Phosphate:  A Defining Metabolite in the Aminoshikimate Pathway

  摘要：

  With respect to the source of the nitrogen atom incorporated into the aminoshikimate pathway, d-erythrose 4-phosphate has been proposed to undergo a transamination reaction resulting in formation of 1-deoxy-1-imino-d-erythrose 4-phosphate. Condensation of this metabolite with phosphoenolpyruvate catalyzed by aminoDAHP synthase would then hypothetically form the 4-amino-3,4-dideoxy-d-arabino-heptulosonic acid 7-phosphate (aminoDAHP), which is the first committed intermediate of the aminoshikimate pathway. However, in vitro formation of aminoDAHP has not been observed. In this account, the possibility is examined that 3-amino-3-deoxy-d-fructose 6-phosphate is the source of the nitrogen atom of the aminoshikimate pathway. Transketolase-catalyzed ketol transfer from 3-amino-3-deoxy-d-fructose 6-phosphate to d-ribose 5-phosphate would hypothetically release 1-deoxy-1-imino-d-erythrose 4-phosphate. Along these lines, a chemoenzymatic synthesis of 3-amino-3-deoxy-d-fructose 6-phosphate was elaborated. Incubation of 3-amino-3-deoxy-d-fructose 6-phosphate in Amycolatopsis mediterranei crude cell lysate with d-ribose 5-phosphate and phosphoenolpyruvate resulted in the formation of aminoDAHP and 3-amino-5-hydroxybenzoic acid. 3-[15N]-Amino-3-deoxy-d-6,6-[2H2]-fructose 6-phosphate was also synthesized and similarly incubated in A. mediterranei crude cell lysate. Retention of both 15N and 2H2 labeling in product aminoDAHP indicates that 3-amino-3-deoxy-d-fructose 6-phosphate is serving as a sequestered form of 1-deoxy-1-imino-d-erythrose 4-phosphate.

  DOI：

  10.1021/ja016963v
• 作为产物：
  描述：

  Shi's ketone 在 lithium aluminium tetrahydride 、 盐酸羟胺 、 sodium acetate 作用下， 以 四氢呋喃 、 水 、 乙腈 为溶剂， 反应 6.0h， 生成 1,2:4,5-di-O-isopropylidene-3-amino-3-deoxy-β-D-fructopyranose
  参考文献：
  名称：

  Biosynthesis of 1-Deoxy-1-imino-d-erythrose 4-Phosphate:  A Defining Metabolite in the Aminoshikimate Pathway

  摘要：

  With respect to the source of the nitrogen atom incorporated into the aminoshikimate pathway, d-erythrose 4-phosphate has been proposed to undergo a transamination reaction resulting in formation of 1-deoxy-1-imino-d-erythrose 4-phosphate. Condensation of this metabolite with phosphoenolpyruvate catalyzed by aminoDAHP synthase would then hypothetically form the 4-amino-3,4-dideoxy-d-arabino-heptulosonic acid 7-phosphate (aminoDAHP), which is the first committed intermediate of the aminoshikimate pathway. However, in vitro formation of aminoDAHP has not been observed. In this account, the possibility is examined that 3-amino-3-deoxy-d-fructose 6-phosphate is the source of the nitrogen atom of the aminoshikimate pathway. Transketolase-catalyzed ketol transfer from 3-amino-3-deoxy-d-fructose 6-phosphate to d-ribose 5-phosphate would hypothetically release 1-deoxy-1-imino-d-erythrose 4-phosphate. Along these lines, a chemoenzymatic synthesis of 3-amino-3-deoxy-d-fructose 6-phosphate was elaborated. Incubation of 3-amino-3-deoxy-d-fructose 6-phosphate in Amycolatopsis mediterranei crude cell lysate with d-ribose 5-phosphate and phosphoenolpyruvate resulted in the formation of aminoDAHP and 3-amino-5-hydroxybenzoic acid. 3-[15N]-Amino-3-deoxy-d-6,6-[2H2]-fructose 6-phosphate was also synthesized and similarly incubated in A. mediterranei crude cell lysate. Retention of both 15N and 2H2 labeling in product aminoDAHP indicates that 3-amino-3-deoxy-d-fructose 6-phosphate is serving as a sequestered form of 1-deoxy-1-imino-d-erythrose 4-phosphate.

  DOI：

  10.1021/ja016963v
• 作为试剂：
  描述：

  1-(4-甲氧苯基)-2-硝基乙烯 、 环己酮 在 1,2:4,5-di-O-isopropylidene-3-amino-3-deoxy-β-D-fructopyranose 作用下， 以 neat (no solvent) 为溶剂， 反应 96.0h， 以31%的产率得到
  参考文献：
  名称：

  对映选择性氨基催化：由D-果糖衍生的单官能伯胺催化将未活化的酮加成至硝基烯烃

  摘要：

  摘要由于迈克尔受体中的亲电子前手性碳远离催化剂的立体定向基团这一事实，因此认为有机催化不对称迈克尔加成反应是最广泛研究的，但仍具有挑战性的立体选择性反应。尽管有关于使用单官能仲胺的迈克尔加成反应中的立体选择性有机催化的报道，但迄今为止尚未报道将单官能伯胺用于所述反应。实际上，尚未报道用于合成（-upgamma）-硝基羰基化合物的单官能氨基催化剂。在这里，我们报道了我们对映选择性迈克尔加成不同酮类由单官能伯胺（催化的硝基烯烃的初步结果1衍生自）d-果糖。 图形概要第一次使用单官能伯胺作为催化剂，将不同的酮与硝基烯烃进行立体选择性迈克尔加成反应，以合成\（upgamma）-硝基羰基化合物。

  DOI：

  10.1007/s12039-017-1371-6

文献信息

• Monofunctional primary amine: A new class of organocatalyst for asymmetric Aldol reaction
  作者：KHIANGTE VANLALDINPUIA、PORAG BORA、GHANASHYAM BEZ

  DOI：10.1007/s12039-017-1237-y

  日期：2017.3

  organocatalysts involving a primary amine as the only functional group is developed for catalytic asymmetric aldol reaction of cyclohexanone/cyclopentanone with various aryl aldehydes in the presence of benzoic acid as an additive at −10∘C. In an unexpected observation, the primary amine catalyzed reactions gave excellent yield and good to excellent stereoselectivity, while secondary amines were found to have

  在-10 ° C的条件下，在苯甲酸作为添加剂存在的情况下，开发了一种新型的有机催化剂，其中以伯胺为唯一的官能团，用于环己酮/环戊酮与各种芳基醛的催化不对称醛醇缩合反应。伯胺催化的反应具有出色的收率和良好的立体选择性，而在相似的反应条件下，仲胺的反应性很小或没有。 一类新的与伯胺作为唯一的催化活性官能团aminocatalysts的混合物用于与苯甲酸的存在作为添加剂在-10各种芳基醛的环己酮/环戊酮的不对称催化醛醇缩合反应开发ö整齐的条件下下进行。
• An Excellent Method for Cbz-protection of Amines
  作者：Khiangte Vanlaldinpuia、H Atoholi Sema、Lalthazuala Rokhum、Ghanashyam Bez

  DOI：10.1246/cl.2010.228

  日期：2010.3.5

  Cbz-protection of aliphatic and aromatic amines can be accomplished with benzylchloroformate using a catalytic amount of dodecatungstophosphoric acid hydrate (0.05 equiv). The reaction is simple, fast, does not require aqueous work-up and gives excellent yields.

  脂肪胺和芳香胺的苄酯保护可以通过使用十二钨磷酸水合物（0.05当量）作为催化剂的苯甲酰氯来实现。该反应简单、迅速，无需水洗处理，并且产率优异。
• Amberlyst-15 Catalyzed Cbz Protection of Amines Under Solvent-Free Conditions
  作者：Pranja P. Bora、Khiangte Vanlaldinpuia、Lalthazuala Rokhum、Ghanashyam Bez

  DOI：10.1080/00397911.2010.515341

  日期：2011.9.15

  Amberlyst-15 can effectively catalyze Cbz protection of aliphatic and aromatic amines within 10-15 min under solvent-free conditions. The catalyst can be used repeatedly without loss of activity, and the reaction requires no workup and gives excellent yields.