1,4-dideoxy-1,4-imino-D-arabitol | 100937-52-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: 1,4-dideoxy-1,4-imino-D-arabitol
• 英文别名: 1,4-dideoxy-1,4-imino-D-arabinitol；DAB；(2R,3R,4R)-2-(hydroxymethyl)pyrrolidine-3,4-diol；DAB-1；(2R,3R,4R)-3,4-dihydroxy-2-hydroxymethylpyrrolidine
• CAS: 100937-52-8
• 化学式: C₅H₁₁NO₃
• 分子量: 133.147
• InChiKey: OQEBIHBLFRADNM-UOWFLXDJSA-N

物化性质

• 熔点：
  113 °C(Solv: methanol (67-56-1); ethyl ether (60-29-7))
• 沸点：
  319.1±37.0 °C(Predicted)
• 密度：
  1.368±0.06 g/cm3(Predicted)
• 稳定性/保质期：
  在常温常压下保持稳定，应避免与强酸或强碱接触。

计算性质

• 辛醇/水分配系数(LogP)：
  -1.7
• 重原子数：
  9
• 可旋转键数：
  1
• 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

安全信息

• WGK Germany：
  3
• 储存条件：
  密封保存，存放在阴凉干燥的仓库中。冷藏温度应保持在2-8°C。

反应信息

• 作为反应物：
  描述：

  1,4-dideoxy-1,4-imino-D-arabitol 在 盐酸 作用下， 以 水 为溶剂， 以80%的产率得到1,4-二脱氧-1,4-亚氨基-D-阿拉伯糖醇盐酸盐
  参考文献：
  名称：

  由d-木糖合成有效的和特定的对映体葡糖苷酶抑制剂，1,4-dideoxy-1,4-imino-d-arabinitol和1,4-dideoxy-1,4-imin

  摘要：

  1，4-二脱氧-1，4-亚氨基阿拉伯糖醇的两种对映体都是葡糖苷酶的特异性抑制剂。1,4-二脱氧-1,4-亚氨基-D-阿拉伯糖醇的合成涉及将木糖的C2和C5与氮连接在一起，而1,4-二脱氧-1.4-亚氨基-L-阿拉伯糖醇的合成需要C1和C4木糖通过氮连接在一起。1,4-Dideoxy-1,4-imino-D-arabinitol是天然存在的吡咯烷生物碱，存在于Standachii蜘蛛和Angylocalyx Boutiqueanus蜘蛛中。

  DOI：

  10.1016/s0040-4020(01)88174-6
• 作为产物：
  描述：

  L-xylopyranose 在 硫酸 、 10 wt% Pd(OH)2 on carbon 、 氢气 、 四丁基碘化铵 、 sodium hydride 、 copper(II) sulfate 、 钯 、 溶剂黄146 、 三乙胺 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙醚 、 二氯甲烷 、 2,2,2-三氟乙醇 为溶剂， -78.0~40.0 ℃ 、101.33 kPa 条件下， 反应 129.5h， 生成 1,4-dideoxy-1,4-imino-D-arabitol
  参考文献：
  名称：

  Diastereoselective concise syntheses of the polyhydroxylated alkaloids DMDP and DAB

  摘要：

  A diastereoselective concise synthesis of the iminosugars DMDP and DAB is presented starting from L-xylose and affording the two alkaloids in good yields of 35% and 22% over seven and eight steps, respectively. The Petasis borono-Mannich reaction of 3,5-di-O-benzyl-L-xylofuranose with benzylamine and (E)-styrylboronic acid served as the nitrogen-introducing key step furnishing the new C-N bond in an entirely diastereoselective manner. A chemo- and regioselective O-mesylation followed by an intramolecular S(N)2-cyclisation allowed the formation of the pyrrolidine ring. Ozonolysis of the styryl double bond and subsequent reduction to form the C-5 hydroxymethyl substituent followed by hydrogenolysis of the benzyl protecting groups concluded the DMDP synthesis. Furthermore, an unexpected fragmentation process during the ozonolysis reaction also gave access to the C-5 decarbinolated DMDP derivative DAB. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2013.11.068

文献信息

• Chirospecific synthesis of 1,4-dideoxy-1,4-imino-D-arabinitol and 1,4-dideoxy-1,4-imino-L-xylitol via one-pot cyclisation
  作者：Jin Hyo Kim、Min Suk Yang、Woo Song Lee、Ki Hun Park

  DOI：10.1039/a803342k

  日期：——

  The multi-protected compounds 4 and 5 were treated with 20% iodine in methanol to give 1,4-dideoxy-1,4-imino-D-arabinitol 1 and 1,4-dideoxy-1,4-imino-L-xylitol 2 directly. Iodine was an efficient catalyst for deprotection of O-isopropylidene, O-(tert-butyldimethylsilyl), N-(9-phenylfluoren-9-yl) and N-benzyloxycarbonyl groups, resulting in intramolecular cyclisation.

  经多重保护的化合物4和5，以20%碘的甲醇溶液处理，直接生成1,4-二去氧-1,4-亚胺基-D-阿拉伯糖醇1和1,4-二去氧-1,4-亚胺基-L-木糖醇2。碘作为高效的催化剂，能够去除O-异丙叉、O-(叔丁基二甲基硅基)、N-(9-苯基芴-9-基)和N-苄氧羰基等保护基团，从而实现分子内环化。
• <scp>D</scp>-Fructose-6-phosphate Aldolase in Organic Synthesis: Cascade Chemical-Enzymatic Preparation of Sugar-Related Polyhydroxylated Compounds
  作者：Alda Lisa Concia、Carles Lozano、José A. Castillo、Teodor Parella、Jesús Joglar、Pere Clapés

  DOI：10.1002/chem.200802532

  日期：2009.4.6

  D‐Fructose‐6‐phosphate aldolase (FSA) is a key biocatalyst for the alternative synthetic construction of biologically active products with known therapeutic and research interest or novel structures relevant to drug discovery. Novel aldol addition reactions of dihydroxyacetone and hydroxyacetone to a variety of aldehydes catalyzed by FSA are presented (see scheme).

  D-果糖-6-磷酸醛缩酶（FSA）是具有已知治疗和研究兴趣或与药物开发相关的新颖结构的生物活性产品的替代合成构造的关键生物催化剂。提出了新颖的二羟基丙酮和羟丙酮与FSA催化的各种醛的醛醇加成反应（参见方案）。
• An <i>in vitro–in vivo</i> sequential cascade for the synthesis of iminosugars from aldoses
  作者：Justyna Kuska、Freya Taday、Kathryn Yeow、James Ryan、Elaine O'Reilly

  DOI：10.1039/d1cy00698c

  日期：——

  Here, we report a chemoenzymatic approach for the preparation of a small panel of biologically important iminosugars from readily available aldoses, employing a transaminase in combination with Gluconobacter oxydans whole cells.

  在这里，我们报告了一种化学酶法，用于从易于获得的醛糖制备一组具有重要生物学意义的亚硝基糖，方法是使用转氨酶与氧化葡萄糖菌全细胞结合。

• HIV protease inhibitors
  申请人：Wong Chi-Huey

  公开号：US06900238B1

  公开（公告）日：2005-05-31

  Combinatorial libraries of HIV and FIV protease inhibitors are characterized by α-keto amide or hydroxyethylamine core structures flanked by on one side by substituted pyrrolidines, piperidines, or azasugars and on the other side by phenylalanine, tyrosine, or substituted tyrosines. The libraries are synthesized via a one step coupling reaction. Highly efficacious drug candidates are identified by screening the libraries for binding and inhibitory activity against both HIV and FIV protease. Drug candidates displaying clinically useful activity against both HIV and FIV protease are identified as being potentially resistive against a loss of inhibitory activity due to development of resistant strains of HIV.

  HIV和FIV蛋白酶抑制剂的组合库以α-酮酰胺或羟乙基胺核心结构为特征，一侧为取代吡咯烷、哌啶或氮代糖，另一侧为苯丙氨酸、酪氨酸或取代酪氨酸。这些库是通过一步偶联反应合成的。通过筛选这些库，识别出对HIV和FIV蛋白酶的结合和抑制活性高效的药物候选化合物。对HIV和FIV蛋白酶都显示出临床有用活性的药物候选化合物被确定为潜在对抗由于HIV耐药株的发展而导致的抑制活性丧失。
• Stereoselective Aldol Additions Catalyzed by Dihydroxyacetone Phosphate-Dependent Aldolases in Emulsion Systems: Preparation and Structural Characterization of Linear and Cyclic Iminopolyols from Aminoaldehydes
  作者：Laia Espelt、Teodor Parella、Jordi Bujons、Conxita Solans、Jesús Joglar、Antonio Delgado、Pere Clapés

  DOI：10.1002/chem.200304966

  日期：2003.10.17

  hydroxyl group originating from the aldehyde. Characterization of the resulting iminocyclitols allowed the assessment of the diastereoselectivity of the enzymatic aldol reactions with respect to the N-protected aminoaldehyde. RAMA formed single diastereoisomers from N-Cbz-glycinal and from both enantiomers of N-Cbz-alaninal, while 14 % of the epimeric product was observed from N-Cbz-3-aminopropanal. Diastereoselectivity

  在许多情况下，磷酸二羟丙酮（DHAP）依赖性醛缩酶催化立体选择性醛缩醛加成的潜力受到受体醛在水/共溶剂混合物中的溶解度的限制。在这里，我们展示了乳液体系作为反应介质的效率，该反应介质是I类果糖-1,6-双磷酸醛缩醛醛糖酶（RAMA）和II类重组鼠李糖-1-磷酸醛糖醛缩醛醛糖酶从DHAP催化的DHAP之间的醛醇加成反应和N-苄氧基羰基（N-Cbz）氨基醛。相对于常规DMF /水混合物，乳液的使用将RAMA催化的羟醛转化率提高了三至十倍。无论反应介质如何，RhuA对N-Cbz氨基醛的反应性都比RAMA高。对于（S）-或（R）-Cbz-丙氨酸，RAMA表现出对R对映体的偏爱，而RhuA没有对映体歧视。将如此获得的线性N-Cbz氨基多元醇进行催化的分子内还原胺化，得到相应的亚氨基环醇。在所有检查的情况下，该反应都是非对映选择性的。面部选择性由源自醛的新形成的羟基的立体化学控制。所得亚氨基环醇的表征

表征谱图