phenyl [(1S,2R,6R,8R,9S)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-8-yl]methyl sulfate | 1269657-64-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机硫酸及其衍生物
• 英文名称: phenyl [(1S,2R,6R,8R,9S)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-8-yl]methyl sulfate
• CAS: 1269657-64-8
• 化学式: C₁₈H₂₄O₉S
• 分子量: 416.449
• InChiKey: WHQMTJRAPGLDFY-LYYZXLFJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  28
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  107
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  phenyl [(1S,2R,6R,8R,9S)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-8-yl]methyl sulfate 在 硫酰氟 、 20% palladium hydroxide-activated charcoal 、 氢气 、 三乙胺 作用下， 以 甲醇 、 aq. phosphate buffer 、 二氯甲烷 、 乙腈 为溶剂， 反应 0.5h， 生成 氟磺酰基氧基苯
  参考文献：
  名称：

  通过硫 (VI) 氟化物交换反应进行 O-硫酸化的一般方法。

  摘要：

  O-硫酸化是生物活性分子中广泛存在的重要化学代码，但携带 O-硫酸盐的复杂生物活性分子的可扩展和简便合成仍然具有挑战性。这里报道的是通过芳基氟硫酸盐和甲硅烷基化羟基之间的硫 (VI) 氟化物交换 (SuFEx) 反应进行 O-硫酸化的一般方法。通过对芳基氟硫酸盐的电子特性进行系统优化，实现了有效的硫酸二酯形成。这种 O-硫酸化策略的多功能性在各种复杂分子的可扩展合成中得到证明，这些分子在不同位置携带硫酸二酯，包括单糖、二糖、氨基酸和类固醇。从硫酸二酯中选择性水解和氢解去除芳基掩蔽基团，以优异的产率得到相应的 O-硫酸盐产物。该策略为合成 O-硫酸盐生物活性化合物提供了强大的工具。

  DOI：

  10.1002/anie.202007211
• 作为产物：
  描述：

  1-(phenoxysulfuryl)-2-methylimidazole 在 N-甲基咪唑 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 3.5h， 生成 phenyl [(1S,2R,6R,8R,9S)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-8-yl]methyl sulfate
  参考文献：
  名称：

  Preparation of trifluoroethyl- and phenyl-protected sulfates using sulfuryl imidazolium salts

  摘要：

  Sulfuryl imidazolium salts (SIS's), a new class of sulfating agents, were prepared bearing the trifluoroethyl (TFE) and phenyl groups, two functionalities that have been used for the protection of sulfate monoesters, by subjecting the corresponding sulfonyl imidazoles with methyl triflate. In contrast, SIS's bearing the electron donating neopentyl and isobutyl groups, two moieties that have also been used for the protection of sulfates, were found to be unstable and could not be isolated though SIS's bearing electron donating aryl groups, such as a p-methoxyphenyl or p-thiomethylphenyl group were readily prepared and are stable compounds. In most instances, TFE-protected phenolic and carbohydrate sulfates were obtained in good yield by reaction of the corresponding SIS's with steroids and carbohydrates. Phenyl-protected carbohydrates were also readily prepared using the corresponding SIS's. Those SIS's having a methyl group at the 2-position of the imidazole ring were, in general, superior sulfating agents to those, which lacked a methyl group at this position. The use of SIS's to prepare TFE-protected sulfates represents a significant improvement of the previous reported procedure, which involved treating unprotected sulfates with trifluorodiazoethane. The TFE protecting group was removed from steroidal sulfates and secondary sulfates in carbohydrates in high yields using NaN(3) in warm DMF, conditions that are less vigorous than those previously reported for removing this group. Deprotection of TFE-protected 6-sulfated carbohydrates using NaN3 in warm DMF proceeded in lower yields due to partial desulfation. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.11.085

文献信息

• Compositions and methods for sulfation of carbohydrates
  申请人：Trustees of Boston College

  公开号：US11505568B1

  公开（公告）日：2022-11-22

  In one aspect, the disclosure relates to a facile strategy to introduce electron-deficient aryl sulfate diesters to silylated hydroxyl groups of carbohydrates and amino acids, among other substrates, wherein selective hydrolysis and the removal of an electron-deficient aromatic group allows for the efficient generation of sulfated carbohydrates, peptides, and other compounds. The incorporation of electron-deficient aryl sulfate diesters in the early stage of the synthesis of glycans, peptides, and the like, disclosed herein avoids time-consuming protecting group manipulations, simplifies the purification of sulfated products, and improves the overall yield and efficiency. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present disclosure.

  在某一方面，本公开涉及一种简便策略，用于向糖类、氨基酸及其他底物的硅化羟基引入电子缺乏的芳基硫酸二酯。通过选择性水解以及去除电子缺乏的芳香基团，可以高效生成硫酸化的糖类、肽类及其他化合物。在糖类、肽类等化合物的合成早期阶段引入电子缺乏的芳基硫酸二酯，如本公开所述，可以避免耗时的保护基操作，简化硫酸化产物的纯化过程，提高整体产率和效率。本摘要旨在作为特定领域中的检索工具，并不旨在限制本公开的内容。
• Preparation of trifluoroethyl- and phenyl-protected sulfates using sulfuryl imidazolium salts
  作者：Ahmed Y. Desoky、Jennifer Hendel、Laura Ingram、Scott Douglas Taylor

  DOI：10.1016/j.tet.2010.11.085

  日期：2011.2

  Sulfuryl imidazolium salts (SIS's), a new class of sulfating agents, were prepared bearing the trifluoroethyl (TFE) and phenyl groups, two functionalities that have been used for the protection of sulfate monoesters, by subjecting the corresponding sulfonyl imidazoles with methyl triflate. In contrast, SIS's bearing the electron donating neopentyl and isobutyl groups, two moieties that have also been used for the protection of sulfates, were found to be unstable and could not be isolated though SIS's bearing electron donating aryl groups, such as a p-methoxyphenyl or p-thiomethylphenyl group were readily prepared and are stable compounds. In most instances, TFE-protected phenolic and carbohydrate sulfates were obtained in good yield by reaction of the corresponding SIS's with steroids and carbohydrates. Phenyl-protected carbohydrates were also readily prepared using the corresponding SIS's. Those SIS's having a methyl group at the 2-position of the imidazole ring were, in general, superior sulfating agents to those, which lacked a methyl group at this position. The use of SIS's to prepare TFE-protected sulfates represents a significant improvement of the previous reported procedure, which involved treating unprotected sulfates with trifluorodiazoethane. The TFE protecting group was removed from steroidal sulfates and secondary sulfates in carbohydrates in high yields using NaN(3) in warm DMF, conditions that are less vigorous than those previously reported for removing this group. Deprotection of TFE-protected 6-sulfated carbohydrates using NaN3 in warm DMF proceeded in lower yields due to partial desulfation. (C) 2010 Elsevier Ltd. All rights reserved.
• A General Approach to <i>O</i> ‐Sulfation by a Sulfur(VI) Fluoride Exchange Reaction
  作者：Chao Liu、Cangjie Yang、Seung Hwang、Samantha L. Ferraro、James P. Flynn、Jia Niu

  DOI：10.1002/anie.202007211

  日期：2020.10.12

  scalable and facile synthesis of complex bioactive molecules carrying O‐sulfates remains challenging. Reported here is a general approach to O‐sulfation by the sulfur(VI) fluoride exchange (SuFEx) reaction between aryl fluorosulfates and silylated hydroxy groups. Efficient sulfate diester formation was achieved through systematic optimization of the electronic properties of aryl fluorosulfates. The versatility

  O-硫酸化是生物活性分子中广泛存在的重要化学代码，但携带 O-硫酸盐的复杂生物活性分子的可扩展和简便合成仍然具有挑战性。这里报道的是通过芳基氟硫酸盐和甲硅烷基化羟基之间的硫 (VI) 氟化物交换 (SuFEx) 反应进行 O-硫酸化的一般方法。通过对芳基氟硫酸盐的电子特性进行系统优化，实现了有效的硫酸二酯形成。这种 O-硫酸化策略的多功能性在各种复杂分子的可扩展合成中得到证明，这些分子在不同位置携带硫酸二酯，包括单糖、二糖、氨基酸和类固醇。从硫酸二酯中选择性水解和氢解去除芳基掩蔽基团，以优异的产率得到相应的 O-硫酸盐产物。该策略为合成 O-硫酸盐生物活性化合物提供了强大的工具。