2-deoxy-D-glucitol | 20847-11-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-deoxy-D-glucitol
• 英文别名: (2R,3S,4R)-hexane-1,2,3,4,6-pentaol；2-deoxi-D-glucitol；D-arabino-2-deoxy-hexitol；arabino-2-Desoxy-D-hexit；2-Desoxy-D-glucit；2-Desoxy-D-mannit；2-Deoxyglucitol；(2R,3S,4R)-hexane-1,2,3,4,6-pentol
• CAS: 20847-11-4
• 化学式: C₆H₁₄O₅
• 分子量: 166.174
• InChiKey: LWWIYCLYWKAKRR-PBXRRBTRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.6
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  101
• 氢给体数：
  5
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-deoxy-D-glucitol 在 Gluconobacter thailandicus NBRC 3254 作用下， 以80%的产率得到5-deoxy-D-threo-hex-2-ulose
  参考文献：
  名称：

  一种简单的合成所有十二种5-脱氧己糖的方法：d-塔格糖3-表异构酶-一种既特异性又通用的试剂

  摘要：

  2-脱氧d -glucitol和2-脱氧d -allitol，既制备由结晶多元醇d -erythronolactone，由被氧化葡糖 thailandicus NBRC 3254至5脱氧d -苏-hexulose [5-脱氧d -果糖= 5脱氧升-sorbose]和5-脱氧d -赤-hexulose [5-脱氧升-psicose = 5脱氧d -tagatose]中。d -Tagatose-3-epimerase（DTE）使5- deoxy - d-果糖平衡为5- deoxy- d - pselose和5-deoxy- 1-戊糖至5-脱氧-1-果糖，为通过醛糖异构酶制备所有八种d-和l -5-脱氧醛己糖提供底物。化学和生物技术方法的这种结合为所有十二种5-脱氧己糖的合成提供了一种简洁的方法，并进一步证明了DTE在其上具有活性的脱氧糖底物的范围。NMR研究表明，5-脱氧d -fructose

  DOI：

  10.1016/j.tetlet.2009.03.061
• 作为产物：
  描述：

  2-Deoxy-D-glucose 在 sodium tetrahydroborate 作用下， 以 水 为溶剂， 反应 16.0h， 生成 2-deoxy-D-glucitol
  参考文献：
  名称：

  A stereochemically general synthesis of 2-deoxyhexoses via the asymmetric allylboration of 2,3-epoxy aldehydes

  摘要：

  A stereochemically general strategy for the synthesis of 2-deoxyhexoses is described. This new approach involves the asymmetric allylboration of epoxy aldehydes 12 and 13, prepared via the Sharpless asymmetric epoxidation reaction, as a means of establishing the stereochemistry of the sugar backbone. Thus, the matched double asymmetric allylborations of 12 and 13 using tartrate allylboronates (R,R)- and (S,S)-7, respectively, provide erythro epoxy alcohols 14 and 16 with excellent diastereoselectivity ( > 96:4) and enantioselectivity (greater-than-or-equal-to 96% ee). The mismatched double asymmetric reactions of 12 and 13 using (S,S)- and (R,R)-7, respectively, provided the diastereomeric threo epoxy alcohols 15 and 17 with lower (ca. 75:25) but still synthetically useful selectivity. The enantiomeric purity of the major diastereomer in each of these reactions was determined to be greater than that of the epoxy aldehyde precursors. Epoxy alcohols 14 and 16 were converted with excellent selectivity to the l-arabino (21) and l-xylo (26) tetrols via neighboring group assisted alpha-substitution reactions of the derived phenylurethane derivatives 18 and 23. Stereochemically complementary beta-opening reactions were accomplished by treating primary alcohols 38, 40, 42, and 44 [prepared from 14-17, respectively, by ethoxyethylation of C(4)-OH and removal of the C(7)-tert-butyldiphenylsilyl (TBDPS) ethers] with NaOH in aqueous t-BuOH at reflux. Acid-catalyzed hydrolysis of the C(4)-ethoxyethyl ethers then provided tetrols d-35 (from 14), d-21 (from 15), d-30 (from 16), and d-26 (from 17), each with excellent stereoselectivity. These tetrols were isolated and fully characterized as the tetraacetate derivatives 36, 22, 31, and 27, respectively. These beta-opening reactions proceed by way of an epoxide migration (29 to 33) that inverts the stereochemistry at C(6) and activates C(7) toward nucleophilic attack. It is necessary that the C(4) hydroxyl be protected in three of the four stereoisomeric series to minimize competitive epoxide migration pathways (cf. 29 to 32a). arabino tetrol 21 and lyxo tetrol 30 were converted to 2-deoxyglucose and 2-deoxygalactose, respectively, by a standard ozonolytic sequence and then to 2-deoxyglucitol pentaacetate (45) and 2-deoxygalactitol pentaacetate (46) via NaBH4 reduction of the 2-deoxy sugars, thereby confirming all stereochemical assignments. The epoxide beta-opening technology was also applied to epoxy benzyl ether 47 (prepared from 14) and epoxy BOM ether 49 (deriving from 16). These reactions provide tetrol derivatives 48 and 50, respectively, in which the C(4)- and C(5)-hydroxyl functionality are suitably differentiated for use in subsequent synthetic sequences.

  DOI：

  10.1021/jo00004a053

文献信息

• Selective C−O Bond Cleavage of Sugars with Hydrosilanes Catalyzed by Piers’ Borane Generated In Situ
  作者：Jianbo Zhang、Sehoon Park、Sukbok Chang

  DOI：10.1002/anie.201708109

  日期：2017.10.23

  [(C6F5)2BH], generated in situ, is demonstrated to promote the hydrosilylative reduction of sugars, providing a series of linear or cyclic polyols with high chemo- and regioselectivities under mild conditions. Studies of catalytic reactivity and regioselectivity with regard to the C−O bond cleavage with hydrosilanes suggest an importance of the steric environment around the anomeric carbon center of the

  Piers的硼烷[（C 6 F 5）2 BH]原位生成，可促进糖的氢化硅烷化还原，在温和条件下提供一系列具有高化学选择性和区域选择性的线性或环状多元醇。关于用氢硅烷裂解C-O键的催化反应性和区域选择性的研究表明，糖异头碳中心周围的空间环境很重要。
• Controlling Sugar Deoxygenation Products from Biomass by Choice of Fluoroarylborane Catalyst
  作者：Youngran Seo、Jared M. Lowe、Michel R. Gagné

  DOI：10.1021/acscatal.9b01578

  日期：2019.8.2

  The feedstocks from biomass are defined and limited by nature, but through the choice of catalyst, one may change the deoxygenation outcome. We report divergent but selective deoxygenation of sugars with triethylsilane (TESH) and two fluoroarylborane catalysts, B(C6F5)3 and B(3,5-CF3)2C6H3)3 (BAr3,5-CF3). To illustrate, persilylated 2-deoxyglucose shows exocyclic C–O bond cleavage/reduction with the

  来自生物质的原料受到自然界的定义和限制，但是通过选择催化剂，可以改变脱氧的结果。我们报告了糖与三乙基硅烷（TESH）和两种氟芳基硼烷催化剂B（C 6 F 5）3和B（3,5-CF 3）2 C 6 H 3）3（BAr 3,5-CF3）的发散性但选择性脱氧）。为了说明这一点，全硅烷基化的2-脱氧葡萄糖显示出环外C–O键的裂解/还原与较少的空间拥挤的BAr 3,5-CF3，而环内的C–O键的裂解/还原则以路易斯酸B（C更多）为主6 F 5）3。取决于催化剂，可以选择性地合成手性呋喃和线性多元醇。机理研究表明，这些催化剂的静止状态是不同的。
• Multiple Forms of Xylose Reductase in <i>Candida intermedia</i>:  Comparison of Their Functional Properties Using Quantitative Structure−Activity Relationships, Steady-State Kinetic Analysis, and pH Studies
  作者：Bernd Nidetzky、Kaspar Brüggler、Regina Kratzer、Peter Mayr

  DOI：10.1021/jf034426j

  日期：2003.12.1

  The xylose-fermenting yeast Candida intermedia produces two isoforms of xylose reductase: one is NADPH-dependent (monospecific xylose reductase; msXR), and another is shown here to prefer NADH approximately 4-fold over NADPH (dual specific xylose reductase; dsXR). To compare the functional properties of the isozymes, a steady-state kinetic analysis for the reaction d-xylose + NAD(P)H + H(+) <--> xylitol

  木糖发酵酵母假丝酵母产生两种木糖还原酶同工型：一种是NADPH依赖性的（单特异性木糖还原酶； msXR），另一种是NADH优于NADPH（双特异性木糖还原酶； dsXR）的4倍。为了比较同工酶的功能特性，对反应中的d-木糖+ NAD（P）H + H（+）<->木糖醇+ NAD（P）（+）进行了稳态动力学分析，并进行了特异性分析测定一系列常数（k（cat）/ K（醛））的常数，以减少一系列侧链大小不同的醛的还原以及与酶的底物结合口袋的氢键结合能力。dsXR弱结合NAD（P）（+）（K（iNAD +）= 70 microM; K（iNADP +）= 55 microM）和NADH（K（i）= 8 microM）大约与NADPH（K（i）= 14 microM）。msXR显示NADPH和NADP（+）的均匀结合（K（iNADP +）大约为K（iNADPH）= 20 microM）。通过将dsXR的对数k（cat）/
• Synthesis of some monodeoxy- and dideoxy-hexitols, and derivatives thereof, from d-glucono-1,5-lactone
  作者：Henk Regeling、Gordon J.F. Chittenden

  DOI：10.1016/0008-6215(90)80145-s

  日期：1990.9

  Syntheses of 2-deoxy-D-arabino-hexitol (1), D-rhamnitol (2), 1,2-dideoxy-D-arabino-hexitol (3), 2,3-dideoxy-D-erythro-hexitol (4), and some derivatives thereof are described. These compounds were obtained by reductive sequences on various compounds formed from methyl 3,4:5,6-di-O-isopropylidene-D-gluconate (9).

  2-脱氧-D-阿拉伯糖醇（1），D-鼠李糖醇（2），1,2-二脱氧-D-阿拉伯糖醇（3），2,3-二脱氧-D-赤藓糖醇（4）的合成），并描述了其一些派生词。这些化合物是通过对3,4：5,6-二-O-异亚丙基-D-葡萄糖酸甲酯形成的各种化合物进行还原序列而获得的（9）。
• From cycloheptatriene to enantiopure sugars: synthesis of 2-deoxyhexoses
  作者：Carl R. Johnson、Adam Golebiowski、Janusz Kozak

  DOI：10.1016/s0008-6215(98)00145-1

  日期：1998.6

  Abstract meso -Diol 3 , prepared from cycloheptatriene, was desymmetrized with Pseudomonas cepacia lipase and isopropenyl acetate to provide enantiopure 4 . The latter, through a series of stereocontrolled oxidation reactions, followed by ring cleavage by ozonolysis and oxidative cleavage of a terminal diol with periodate, provided of 2-deoxy- d - xylo -hexose ( 1 ) and 2-deoxy- d - arabino -hexose

  摘要用假单胞菌脂肪酶和乙酸异丙烯酯对由环庚三烯制得的内消旋二甲酚3进行对称化处理，得到对映体4。后者通过一系列立体控制的氧化反应，然后通过臭氧分解进行环裂解，并用高碘酸盐对末端二醇进行氧化裂解，由2-脱氧-d-木糖-己糖（1）和2-脱氧-d-阿拉伯糖-提供。己糖（2），其特征为相应的醛糖醇五乙酸盐。