1-O-acetyl-2,3:4,6-di-O-isopropylidenemannofuranose | 153541-62-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-O-acetyl-2,3:4,6-di-O-isopropylidenemannofuranose
• 英文别名: acetyl 2,3:5,6-di-O-isopropylidene-D-mannofuranoside；1-O-acetyl-2,3:5,6-di-O-isopropylidenemannofuranose；1-O-acetyl-2,3:5,6-di-O-isopropylidene-D-mannofuranose；(3aS,6R,6aS)-6-((R)-2,2-Dimethyl-1,3-dioxolan-4-yl)-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxol-4-yl acetate；[(3aS,6R,6aS)-6-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-4-yl] acetate
• CAS: 153541-62-9
• 化学式: C₁₄H₂₂O₇
• 分子量: 302.324
• InChiKey: WLHUZRZYXVBFJH-IKQSSVLVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  72.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  1-O-acetyl-2,3:4,6-di-O-isopropylidenemannofuranose 在 三甲基溴硅烷 作用下， 以 二氯甲烷 为溶剂， 生成 2,3:5,6-Di-O-isopropyliden-α-D-mannofuranosyl-bromid
  参考文献：
  名称：

  Rapid Preparation of Variously Protected Glycals Using Titanium(III)

  摘要：

  Glycosyl chlorides and bromides can be rapidly converted to glycals in high yield by reaction with (Cp2Ti[III]Cl)(2). This reagent tolerates a wide range of common carbohydrate protecting groups, including silyl ethers, acetals, and esters; the methodology provides a general route for the preparation of glycals substituted with both acid- and base-labile functionality. A reaction mechanism is proposed that is based on heteroatom abstraction to give an intermediate glycosyl radical. This radical reacts with a second equivalent of Ti(III) to yield a glycosyltitanium(IV) species. P-Heteroatom elimination from the glycosyltitanium(IV) complex gives the glycal.

  DOI：

  10.1021/jo982447k
• 作为产物：
  描述：

  甘露糖 在 吡啶 、 碘 作用下， 反应 2.0h， 生成 1-O-acetyl-2,3:4,6-di-O-isopropylidenemannofuranose
  参考文献：
  名称：

  “Boomerang” Strategy in Carbohydrate Chemistry: Diastereoselective Synthesis of C-Glycosylated Benzothiazoles from ortho-Isocyanophenyl Thioglycosides

  摘要：

  DOI：

  10.1021/acs.orglett.3c03817

文献信息

• A mild and efficient method for chemoselective deprotection of acetonides by bismuth(III) trichloride
  作者：N.Raghavendra Swamy、Y Venkateswarlu

  DOI：10.1016/s0040-4039(02)01809-9

  日期：2002.10

  Acetonides undergo chemoselective deprotection to afford the corresponding 1,2-diols in excellent yields using bismuth trichloride in acetonitrile/dichloromethane at ambient temperature.

  在环境温度下，使用三氯化铋的乙腈/二氯甲烷溶液，对乙酰丙酮进行化学选择性脱保护，以优异的收率得到相应的1,2-二醇。
• Organofluorine compounds and fluorinating agents. Part 11. Glycosyl fluorides from acetal-protected sugars
  作者：Ralf Miethchen、Torsten Gabriel

  DOI：10.1016/0022-1139(93)02938-b

  日期：1994.4

  2,3:5,6-di-O-isopropylidene-d-manno-furanoside (15) with simultaneous conversion into the corresponding acetylated glycosyl fluorides (8, 12, 16). The second acetal function in 11 and 15 is not cleaved by the weakened HF medium. 2-O-Benzyl-protected sugars such as methyl 3,5,6-tri-O-methyl-2-O-benzyl-d-glucofuranoside (13) react intramolecularly in the presence of HF/nitromethane/acetic anhydride to

  2- ø - （2-乙酰氧基乙基）-3,4,6三- ö甲基α-d葡糖基氟化物（5）通过1,2-的部分切割得到ö -ethanediyl-β-D-通过HF /硝基甲烷/乙酸酐体系在糖苷位置上的吡喃葡萄糖衍生物4。相同的介质允许选择性的1,2-异亚丙基函数的α-d-glucofuranosides裂解（7，11）和5,6-的Ó在乙酰2,3-异亚丙基组：5,6-二- ö异亚丙基- d甘露-呋喃糖苷（15）与同时转换成相应的乙酰化的糖基氟化物（8，12，16）。弱化的HF介质不会裂解11和15中的第二个乙缩醛功能。2- ø苯甲基保护的糖，如甲基-3,5,6-三- ö甲基-2- ö苄基d-glucofuranoside（13）在HF的存在下反应，在分子内/硝基甲烷/乙酸酐以形成环状C-糖苷（14）。
• Phosphomolybdic Acid Supported on Silica Gel: An Efficient, Mild and Reusable Catalyst for the Chemoselective Hydrolysis of Acetonides
  作者：J. S. Yadav、S. Raghavendra、M. Satyanarayana、E. Balanarsaiah

  DOI：10.1055/s-2005-872701

  日期：——

  Carbohydrate acetonides were chemoselectively cleaved to the corresponding diols by using environmentally benign phosphomolybdic acid (H3PMo12O40) supported on silica gel (PMA-SiO2) at ambient temperature in a short span of 5-7 minutes in acetonitrile. Acid-labile protective groups such as THP, TBS, TBDPS, MOM, OMe and PMB were found to be stable under the reaction conditions.

  碳水化合物乙缩醛在环境友好的负载型磷钼酸（H3PMo12O40/硅胶，简称PMA-SiO2）作用下，于室温、乙腈溶液中仅需5至7分钟即可选择性地裂解为相应的二醇。在这种反应条件下，如THP、TBS、TBDPS、MOM、OMe和PMB等对酸不稳定的保护基团均能保持稳定。
• Nafion-H mediated selective deprotection of terminal isopropylidene acetals and trityl ethers. Application in the synthesis of a substituted piperidone
  作者：Girish K. Rawal、Shikha Rani、Amit Kumar、Yashwant D. Vankar

  DOI：10.1016/j.tetlet.2006.10.067

  日期：2006.12

  A facile chemoselective hydrolysis of terminal isopropylidene acetals has been achieved in good to excellent yields within 2–4 h using Nafion-H in methanol at ambient temperature. This procedure has been employed to synthesize a substituted piperidone derivative. Similarly, trityl ethers are also deprotected to the corresponding alcohols in excellent yields using Nafion-H at room temperature.

  在环境温度下，使用Nafion-H在甲醇中的2-4小时内，可以轻松实现末端异亚丙基缩醛的化学选择性水解，并且收率很好。该方法已用于合成取代的哌啶酮衍生物。类似地，在室温下，使用Nafion-H，三苯甲基醚也以优异的产率脱保护为相应的醇。
• Chemoselective hydrolysis of terminal isopropylidene acetals in acetonitrile using molecular iodine as a mild and efficient catalyst
  作者：J.S. Yadav、M. Satyanarayana、S. Raghavendra、E. Balanarsaiah

  DOI：10.1016/j.tetlet.2005.10.043

  日期：2005.12

  A simple, mild and efficient method for deprotection of acetonides in the presence of molecular iodine is described. Acid labile protecting groups such as PMB, OMe, OBn, allyl and propargyl are compatible with the reaction conditions, while TBS, TBDPS, TMS and THP ethers were unstable under the same conditions.

  描述了一种在分子碘存在下使丙酮化物脱保护的简单，温和和有效的方法。酸不稳定的保护基（如PMB，OMe，OBn，烯丙基和炔丙基）与反应条件兼容，而TBS，TBDPS，TMS和THP醚在相同条件下不稳定。