3-O-[(t-butyl)dimethylsilyl]-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose | 99605-27-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-O-[(t-butyl)dimethylsilyl]-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose
• 英文别名: 3-O-(ter-butyldimethylsilyl)-1,2:5,6-O-isopropylidene-α-D-glucofuranose；3-O-tert-butyldimethylsilyl-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose；3-O-[(1,1-Dimethylethyl)dimethylsilyl]-1,2:5,6-bis-O-(1-methylethylidene)-alpha-D-glucofuranose；[(3aR,5R,6S,6aR)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-6-yl]oxy-tert-butyl-dimethylsilane
• CAS: 99605-27-3
• 化学式: C₁₈H₃₄O₆Si
• 分子量: 374.55
• InChiKey: LFPYKSVBKNNGCK-UXXRCYHCSA-N

物化性质

• 沸点：
  377.8±42.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)
• 溶解度：
  可溶于二氯甲烷；氯仿；乙酸乙酯;

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3-O-[(t-butyl)dimethylsilyl]-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose 在 bismuth(III) chloride 、 水 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 以90%的产率得到3-O-[(t-butyl)dimethylsilyl]-1,2-O-isopropylidene-α-D-glucofuranose
  参考文献：
  名称：

  一种温和有效的三氯化铋（III）化学选择性脱除丙酮化物的方法

  摘要：

  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。

  DOI：

  10.1016/s0040-4039(02)01809-9
• 作为产物：
  描述：

  3-O-benzoyl-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose 在 咪唑 、 三乙胺 作用下， 以 甲醇 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.42h， 生成 3-O-[(t-butyl)dimethylsilyl]-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose
  参考文献：
  名称：

  RAPID CARBOHYDRATE PROTECTING GROUP MANIPULATIONS ASSISTED BY MICROWAVE DIELECTRIC HEATING

  摘要：

  The protocols for oligosaccharide synthesis are often tedious due to extended synthetic routes and reaction times. We herein describe methods assisted by microwave dielectric heating, which enable very short reaction times and high yields for the introduction and removal of eleven of the most commonly used protecting groups in carbohydrate syntheses. Several examples are reported, where solid supported reagents in combination with microwave dielectric heating have been used. This results in both faster and easier synthesis and purification.

  DOI：

  10.1081/car-100105712

文献信息

• Total synthesis of a protected form of sphingofungin E using the [3,3]-sigmatropic rearrangement of an allylic thiocyanate as the key reaction
  作者：Miroslava Martinková、Jozef Gonda、Jana Špaková Raschmanová、Michaela Slaninková、Juraj Kuchár

  DOI：10.1016/j.carres.2010.09.016

  日期：2010.11

  An approach to the stereocontrolled synthesis of the protected form of sphingofungin E (32) starting from the known protected d-glucose derivative 3 is described herein. For the construction of a tetrasubstituted carbon atom that is substituted with nitrogen, the [3,3]-sigmatropic rearrangement of thiocyanate 8 was employed. Subsequent functional group interconversions afforded the highly functionalized

  本文描述了从已知的被保护的d-葡萄糖衍生物3开始的立体控制合成的鞘氨醇单蛋白E（32）的保护形式的方法。为了构造被氮取代的四取代的碳原子，使用了硫氰酸酯8的[3，3]-σ重排。随后的官能团相互转化提供了高度官能化的片段，烯丙基溴26。其与已知的C（12）疏水链段2的偶联反应，然后进行进一步的操作，完成了总合成。
• Selective deprotection of terminal isopropylidene acetals and trityl ethers using HClO4 supported on silica gel
  作者：Aditi Agarwal、Yashwant D. Vankar

  DOI：10.1016/j.carres.2005.04.005

  日期：2005.7

  Terminal isopropylidene acetals are selectively cleaved to the corresponding 1,2-diols in good to excellent yields in 6-24 h at room temperature by using the 'HClO4.SiO2' reagent system. Likewise, trityl ethers are readily cleaved to the corresponding alcohols in good to excellent yields within 2-3 h at room temperature. Work-up involves merely filtration of the reagent followed by purification of

  通过使用'HClO4.SiO2'试剂系统，在室温下于6-24小时内将末端异亚丙基缩醛以良好至极好的收率选择性裂解为相应的1,2-二醇。同样，在室温下2-3小时内，三苯甲基醚很容易以良好或优异的收率裂解成相应的醇。后处理仅涉及试剂的过滤，然后纯化粗产物。
• Synthesis of imidazo[2,1-b]thiazoles linked to an unprotected carbohydrate moiety
  作者：José Sebastián Barradas、María Inés Errea、Norma Beatriz D’Accorso

  DOI：10.1016/j.carres.2012.04.011

  日期：2012.7

  series of imidazo[2,1-b]thiazoles substituted on C-3 or C-5 with an unprotected carbohydrate moiety were synthesized. Different protective groups for position 3 of the carbohydrate moiety were tested (acetyl, tert-butyldimethylsilyl (TBDMS), and p-methoxybenzyl (PMB)) and the latter turn out to be the best strategy to obtain the desired products. Full deprotection of the carbohydrate was performed successfully

  合成了两个系列的在C-3或C-5上被未保护的碳水化合物部分取代的咪唑并[2,1-b]噻唑。测试了碳水化合物部分3位的不同保护基（乙酰基，叔丁基二甲基甲硅烷基（TBDMS）和对甲氧基苄基（PMB）），事实证明，后者是获得所需产品的最佳策略。仅一步就成功地完成了碳水化合物的完全脱保护。
• Claisen Rearrangements of 5,6-Dideoxy-1,2-<i>O</i>-isopropylidene-α-D-<i>xylo</i>- and α-D-<i>ribo</i>-hept-5-eno-1,4-furanoses with Triethyl Orthoacetate
  作者：Kin-ichi Tadano、Kei-ichi Shimada、Akiko Miyake、Jun Ishihara、Seiichiro Ogawa

  DOI：10.1246/bcsj.62.3978

  日期：1989.12

  The (E)- and (Z)-isomers (2E and 2Z) of 3-O-benzyl-5,6-dideoxy-1,2-O-isopropylidene-α -d-xylo-hept-5-eno-1,4-furanose were subjected to Claisen rearrangement with triethyl orthoacetate. Possible two diastereomers were obtained as a 1 to 1 mixture from both of 2Z and 2E, and also from their 3-hydroxy or 3-siloxy derivatives. On the other hand, the rearrangement of the corresponding d-ribo derivative (13Z) and its 3-O-(t-butyldiphenylsilyl) derivative proceeded with a high level of diastereoselectivity. By contrast, the (E)-isomer of 13Z showed no significant stereoselectivity, resulting in the formation of a diastereomeric mixture. The configurations of the introduced stereogenic centers by the rearrangements were unambiguously established by chemical transformations.

  3-O-苄基-5,6-二脱氧-1,2-O-异亚丙基-α-d-呋喃木-5-烯糖-1,4-糖的（E）和（Z）异构体（2E和2Z）与三乙基原甲酸酯进行了克莱森重排反应。从2Z和2E以及它们的3-羟基或3-硅氧基衍生物中，得到了可能的两种非对映异构体的1:1混合物。另一方面，相应的d-呋喃核糖衍生物（13Z）及其3-O-（叔丁基二苯基硅基）衍生物的重排反应具有高度的非对映选择性。相比之下，13Z的（E）异构体显示出较弱的立体选择性，形成了非对映异构体混合物。通过化学转化明确确定了重排引入的手性中心的构型。
• Study of Stereoselectivity in Organometallic Additions to 1,2-O-Isopropylidene-O-R-α-D-xylopentodialdo-1,4-furanose
  作者：Tibor Gracza、Peter Szolcsányi

  DOI：10.3390/51201386

  日期：——

  yielded the required bicyclic skeletonswith high regio-preference and excellent threo-selectivity (concerning the newly formed stereocentreat C-3) [4,5], Grignard addition of phenyl magnesium bromide to 6a in tetrahydrofuran led to twodiastereomeric alcohols 7a and 8a in a 1:3 ratio favouring formation of the L-ido diastereomer 8a,possessing the correct stereochemistry for less cytotoxic 7-epi-goniofufurone

  Tibor Gracza* 和 Peter Szolcsanyi 斯洛伐克理工大学化学技术学院有机化学系，斯洛伐克布拉迪斯拉发 Sk-812 37。电话。(0421) 7 59325 167，传真 [phone]，http://www.chtf.stuba.sk/KATEDRY/koch/new_gracza.htm* 通讯作者。?-mail [e-mail]: 2 August 2000 / Accepted: 8 December 2000 / Published: 21 December 2000 摘要：将有机金属试剂添加到 1,2-O-异亚丙基-OR-α- 的非对映选择性研究了 D-xylopentodialdo-1,4-呋喃糖 (6)。关键词: 有机金属试剂, 立体选择性, 羰基的加成。 简介 角呋喃酮 (+)-1