1,5,6-trideoxy-1,5-imino-L-mannitol | 135395-45-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: 1,5,6-trideoxy-1,5-imino-L-mannitol
• 英文别名: (2S,3S,4S,5S)-2-methylpiperidine-3,4,5-triol
• CAS: 135395-45-8
• 化学式: C₆H₁₃NO₃
• 分子量: 147.174
• InChiKey: VYOCYWDJTQRZLC-BXKVDMCESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.9
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  72.7
• 氢给体数：
  4
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  6-deoxy-2,3-O-isopropylidene-L-talono-1,4-lactone 在 palladium on activated charcoal 吡啶 、 sodium azide 、 dimethyl sulfide borane 、 Amberlite IRA-400 (OH^(1-)) 、 氢气 、 三氟乙酸 、 sodium nitrite 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 14.5h， 生成 1,5,6-trideoxy-1,5-imino-L-mannitol
  参考文献：
  名称：

  Washiyama, Susumu; Kamiya, Akihiko; Esaki, Sachiko, Bioscience, Biotechnology and Biochemistry, 1993, vol. 57, # 5, p. 847 - 849

  摘要：

  DOI：

文献信息

• Asymmetric routes to azasugars from chiral bicyclic lactams. Synthesis of 1,4-dideoxy-1,4-imino-D-lyxitol; L-deoxymannojirimycin; rhammo-1-deoxynojirimycin and 1-deoxy-6-epicastanospermine
  作者：A.I Meyers、Charles J Andres、James E Resek、Charlotte C Woodall、Maureen A McLaughlin、Peter H Lee、David A Price

  DOI：10.1016/s0040-4020(99)00454-8

  日期：1999.7

  By employing the appropriate chiral bicyclic lactams, the asymmetric total synthesis of four enantiopure azasugars mentioned in the title were successfully achieved. A series of diastereoselective oxidations () followed by diastereoselective reductions (BH3, 9-BBN) gave good yields of the trisubstituted (16) and tetrasubstituted (2,3,4) pyrrolidine and piperidines respectively.

  通过使用合适的手性双环内酰胺，成功实现了标题中提到的四种对映纯氮杂糖的不对称全合成。一系列非对映选择性氧化（的），接着加入非对映选择性的减少（BH 3，9-BBN），得到三取代（的良好产率16）和四取代的（2,3,4）吡咯烷和哌啶分别。
• Total synthesis of pipecolic acid and 1-<i>C</i>-alkyl 1,5-iminopentitol derivatives by way of stereoselective aldol reactions from (<i>S</i>)-isoserinal
  作者：Sebastian Baś、Rafał Kusy、Monika Pasternak-Suder、Cyril Nicolas、Jacek Mlynarski、Olivier R. Martin

  DOI：10.1039/c7ob02797d

  日期：——

  A short synthesis of iminosugars and pipecolic acid derivatives has been realized through aldol addition of a pyruvate, a range of ketones and (S)-isoserinal, followed by catalytic reductive intramolecular amination. The stereoselective aldol reaction was achieved successfully by using tertiary amines or di-zinc aldol catalysts, thus constituting two parallel routes to optically pure products with

  亚氨基糖和胡椒酸衍生物的简短合成已通过醛醇添加丙酮酸酯，一系列酮和（S）-异丝氨酸的醛醇缩合，然后进行催化还原性分子内胺化来实现。通过使用叔胺或二锌羟醛催化剂成功地完成了立体选择性羟醛反应，从而构成了两条平行路线，以高收率和高非对映选择性获得光学纯的产物。这些碳水化合物类似物可能是有效的糖苷酶和糖基转移酶的抑制剂。
• Organocatalytic<i>syn</i>-Aldol Reactions of Hydroxy Ketones with (<i>S</i>)-Isoserinal: Asymmetric Synthesis of 6-Deoxy-1,5-iminohexitols and Related Compounds
  作者：Cyril Nicolas、Roman Pluta、Monika Pasternak-Suder、Olivier R. Martin、Jacek Mlynarski

  DOI：10.1002/ejoc.201201413

  日期：2013.3

  intermediate was reacted through organocatalyzed aldol reaction or Wittig based chain extension and functionalization to give enantiopure 1,5,6-trideoxy-1,5-imino-hexitols such as 10a (L-manno) and 10b (D-gluco). These two compounds are of interest as glycosidase inhibitors. The elaborated organocatalytic process includes diastereoselective syn aldol reaction of (S)-isoserinal hydrate and hydroxyacetone or

  报道了一种改进且方便的大规模保护 (S)-异丝氨酸制备方法。该关键中间体通过有机催化的羟醛反应或基于 Wittig 的扩链和官能化反应，得到对映体纯的 1,5,6-trideoxy-1,5-imino-hexitols，如 10a (L-manno) 和 10b (D-gluco)。这两种化合物可用作糖苷酶抑制剂。精心设计的有机催化过程包括 (S)-异丝氨酸水合物与羟基丙酮或 1-羟基-2-辛酮的非对映选择性合成羟醛反应，并由各种基于氨基酸的催化剂促进。实现了高达 8:1 的非对映选择性，从而为这些重要的碳水化合物模拟物建立了一条新的、有效的合成路线。
• Alternative synthesis and antibacterial evaluation of 1,5-dideoxy-1,5-imino-l-rhamnitol
  作者：Suresh Dharuman、Yichen Wang、David Crich

  DOI：10.1016/j.carres.2015.10.015

  日期：2016.1

  A convenient synthesis is described of 5-azido-5-deoxy-2,3-O-isopropylidene-l-rhamnofuranose from l-rhamnose in seven steps and 17% overall yield. A key feature of the synthesis is the selective oxidation of the secondary alcohol in 2,3-O-isopropylidene-l-rhamnofuranose in the presence of the hemiacetal to give the corresponding ketone in good yield using the Parikh-Doering reagent. 5-Azido-5-deoxy-2

  描述了从1-鼠李糖以七个步骤和17％的总收率方便地合成5-叠氮基5-脱氧-2,3-O-异亚丙基-1-鼠李呋喃糖的方法。合成的关键特征是在半缩醛存在下，在2,3-O-异亚丙基-1-鼠李呋喃糖中选择性氧化仲醇，从而使用Parikh-Doering试剂以高收率得到相应的酮。然后通过文献方法将5-叠氮基5-脱氧-2,3-O-异亚丙基-1-鼠李呋喃糖转化为1,5-二脱氧-1,5-亚氨基-1-鼠李糖醇对铜绿假单胞菌，耐甲氧西林的金黄色葡萄球菌和大肠杆菌具有抗菌活性。
• Use of dihydroxyacetone phosphate-dependent aldolases in the synthesis of deoxy aza sugars
  作者：Kevin K. C. Liu、Tetsuya Kajimoto、Lihren Chen、Ziyang Zhong、Yoshitaka Ichikawa、Chi Huey Wong

  DOI：10.1021/jo00022a013

  日期：1991.10

  The use of fructose-1,6-diphosphate (FDP), fuculose-1-phosphate (Fuc-1-P) and rhamnulose-1-phosphate (Rham-1-P) aldolases in organic synthesis is described. Fuc-1-P, Rham-1-P, and their phosphate-free species have been prepared and characterized. Both Fuc-1-P and Rham-1-P aldolases accept 3-azido-2-hydroxypropanal as a substrate to form L-omega-azidoketose phosphates, which upon dephosphorylation and hydrogenolysis on Pd/C, gave 1-deoxyazasugars structurally related to D-galactose and L-mannose. Hydrogenolysis of the enzyme products azidoketose 1-phosphates, however, gave 1,6-dideoxyazasugars structurally related to 6-deoxygalactose and L-rhamnose. Explanations for the stereoselectivity in the hydrogenolysis reactions were provided. Similarly, FDP aldolase catalyzed the aldol condensation reaction with 2-azido-3-hydroxypropanal to afford a new synthesis of 2(R),5(S)-bis(hydroxymethyl)-3(R),4(R)-dihydroxypyrrolidine, a potent inhibitor of a number of glycosidases. A new empirical formula is developed to relate the inhibition constants and inhibitor binding for alpha- and beta-glucosidases.