Acetic acid (2R,3R,4S,5R,6R)-2-acetoxymethyl-4,5-bis-methoxycarbonyloxy-6-(2,2,2-trichloro-acetimidoyloxy)-tetrahydro-pyran-3-yl ester | 368884-86-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Acetic acid (2R,3R,4S,5R,6R)-2-acetoxymethyl-4,5-bis-methoxycarbonyloxy-6-(2,2,2-trichloro-acetimidoyloxy)-tetrahydro-pyran-3-yl ester
• 英文别名: [(2R,3R,4S,5R,6R)-3-acetyloxy-4,5-bis(methoxycarbonyloxy)-6-(2,2,2-trichloroethanimidoyl)oxyoxan-2-yl]methyl acetate
• CAS: 368884-86-0
• 化学式: C₁₆H₂₀Cl₃NO₁₂
• 分子量: 524.693
• InChiKey: MCOZOBFYXMKRGP-RMPHRYRLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  32
• 可旋转键数：
  13
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  166
• 氢给体数：
  1
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  双丙酮半乳糖 、 Acetic acid (2R,3R,4S,5R,6R)-2-acetoxymethyl-4,5-bis-methoxycarbonyloxy-6-(2,2,2-trichloro-acetimidoyloxy)-tetrahydro-pyran-3-yl ester 在 ytterbium(III) triflate 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以85%的产率得到Acetic acid (2R,3R,4S,5R,6R)-2-acetoxymethyl-4,5-bis-methoxycarbonyloxy-6-((3aR,5R,5aS,8aS,8bR)-2,2,7,7-tetramethyl-tetrahydro-bis[1,3]dioxolo[4,5-b;4',5'-d]pyran-5-ylmethoxy)-tetrahydro-pyran-3-yl ester
  参考文献：
  名称：

  Activation of disarmed 2-O-alkoxycarbonylated glycosyl trichloroacetimidates with lanthanide triflates: an efficient approach for the synthesis of 1,2-trans glycosides

  摘要：

  Disarmed glycosyl trichloroacetimidates can be activated by Yb(OTf)(3) in the synthesis of 1.2-trans glycosides involving primary and secondary acceptors. Concurrent formation of orthoester side products can be avoided by the use of alkoxycarbonyl groups for the protection of the donor 2-hydroxyl. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)01158-3
• 作为产物：
  描述：

  [(2R,3R,4S,5R)-3,6-diacetyloxy-4,5-bis(methoxycarbonyloxy)oxan-2-yl]methyl acetate 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 苄胺 作用下， 以 四氢呋喃 为溶剂， 反应 7.0h， 生成 Acetic acid (2R,3R,4S,5R,6R)-2-acetoxymethyl-4,5-bis-methoxycarbonyloxy-6-(2,2,2-trichloro-acetimidoyloxy)-tetrahydro-pyran-3-yl ester
  参考文献：
  名称：

  Activation of disarmed 2-O-alkoxycarbonylated glycosyl trichloroacetimidates with lanthanide triflates: an efficient approach for the synthesis of 1,2-trans glycosides

  摘要：

  Disarmed glycosyl trichloroacetimidates can be activated by Yb(OTf)(3) in the synthesis of 1.2-trans glycosides involving primary and secondary acceptors. Concurrent formation of orthoester side products can be avoided by the use of alkoxycarbonyl groups for the protection of the donor 2-hydroxyl. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)01158-3

文献信息

• Iodine/Triethylsilane as a Convenient Promoter System for the Activation of Disarmed Glycosyl Trichloro- and N-(Phenyl)trifluoroacetimidates
  作者：Matteo Adinolfi、Gaspare Barone、Alfonso Iadonisi、Marialuisa Schiattarella

  DOI：10.1055/s-2002-19770

  日期：——

  Disarmed glycosyl trichoro- and N-(phenyl)trifluoroacetimidates can be efficiently activated by the combined reagent system I2/Et3SiH in the fast and high yielding glycosylation of primary and secondary saccharidic acceptors.

  经去活化的糖基三氯-和N-（苯基）三氟乙酰亚胺可通过I2/Et3SiH复合试剂体系高效活化，在快速且高产率的条件下，实现对初级和次级糖类受体的糖基化反应。
• Activation of Glycoyl Trihaloacetimidates with Acid-Washed Molecular Sieves in the Glycosidation Reaction
  作者：Matteo Adinolfi、Gaspare Barone、Alfonso Iadonisi、Marialuisa Schiattarella

  DOI：10.1021/ol027353i

  日期：2003.4.1

  [reaction: see text] Commercially available 4 A acid washed molecular sieves (4 A AW 300 MS) are efficient activators of glycosyl trichloro- and N-phenyltrifluoroacetimidates. These promoters allow glycosidation of primary and secondary saccharidic acceptors to be performed in high yield, under very mild conditions and by an experimentally simple procedure. In addition, the recyclability of such promoters

  [反应：见正文]市售的4 A酸洗分子筛（4 A AW 300 MS）是糖基三氯和N-苯基三氟乙酰亚氨酸酯的有效活化剂。这些启动子允许在非常温和的条件下和通过实验简单的程序以高收率进行一级和二级糖受体的糖基化。另外，还已经证明了此类启动子的可回收性。
• Regioselective Phenol or Carbinol Glycosidation of 17β-Estradiol and Derivatives Thereof
  作者：Alfonso Iadonisi、Matteo Adinolfi、Alessandro Pezzella、Alessandra Ravidà

  DOI：10.1055/s-2005-871930

  日期：——

  Unprecedented regioselective glycosidations of 17b-estradiol and nitro substituted derivatives thereof either at the phenol or carbinol position is reported. In the former case, glycosyl bromides or iodides were employed as the donors in a base promoted reaction conducted under two-phase conditions. In the latter case, glycosyl trichloroacetimidate donors were used in combination with the mild activation of 4 Å acid washed molecular sieves.

  据报道，17b-雌二醇及其硝基取代的衍生物在苯酚或卡宾醇位置上发生了前所未有的区域选择性糖苷化反应。在前一种情况下，在两相条件下进行的碱促进反应中，使用了溴化或碘化糖基作为供体。在后一种情况下，使用了三氯乙酰亚氨酸糖基供体，并结合 4 Å 酸洗分子筛的温和活化。
• Remarkably efficient activation of glycosyl trichloro- and (N-phenyl)trifluoroacetimidates with bismuth(III) triflate
  作者：Matteo Adinolfi、Alfonso Iadonisi、Alessandra Ravidà、Silvia Valerio

  DOI：10.1016/j.tetlet.2006.02.034

  日期：2006.4

  Easily handled and nontoxic Bi(OTf)(3) is a powerful activator for trichloro- and (N-phenyl)trifluoroacetimidate glycosyl donors. This catalyst allows glycosidations to be performed at low temperatures in very short times. Rewarding yields were obtained from a wide range of donors of varying reactivity. (c) 2006 Elsevier Ltd. All rights reserved.
• Efficient activation of glycosyl N-(phenyl)trifluoroacetimidate donors with ytterbium(III) triflate in the glycosylation reaction
  作者：Matteo Adinolfi、Gaspare Barone、Alfonso Iadonisi、Marialuisa Schiattarella

  DOI：10.1016/s0040-4039(02)01124-3

  日期：2002.8

  The mild, moisture-stable and cheap catalyst Yb(OTf)(3) activates glycosyl N-(phenyl)trifluoroacetimidates in the stereoselective synthesis of 1,2-trans and 1,2-cis glycosides. A suitable choice of the reaction solvent led to good yields and stereoselectivity ratios. The protocol was successfully applied to acceptors and donors both exhibiting a wide range of reactivity. (C) 2002 Published by Elsevier Science Ltd.