[(2R,3S,4S,5R,6S)-3,4,5-triacetyloxy-6-[3-(4-methoxyphenyl)-8-methyl-4-oxochromen-7-yl]oxyoxan-2-yl]methyl acetate | 1309445-42-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 异黄酮类化合物
• 英文名称: [(2R,3S,4S,5R,6S)-3,4,5-triacetyloxy-6-[3-(4-methoxyphenyl)-8-methyl-4-oxochromen-7-yl]oxyoxan-2-yl]methyl acetate
• CAS: 1309445-42-8
• 化学式: C₃₁H₃₂O₁₃
• 分子量: 612.587
• InChiKey: GQOJMDSZNNCAKS-PLZPULBCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  44
• 可旋转键数：
  13
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  159
• 氢给体数：
  0
• 氢受体数：
  13

反应信息

• 作为产物：
  描述：

  7-hydroxy-3-(4-methoxyphenyl)-8-methyl-4H-chromen-4-one 、 2,3,4,6-四乙酰氧基-alpha-D-吡喃糖溴化物 在 C₁₆H₂₈AgN₄⁽¹⁺⁾ 、 苄基三乙基氯化铵 作用下， 反应 3.33h， 以76%的产率得到[(2R,3S,4S,5R,6S)-3,4,5-triacetyloxy-6-[3-(4-methoxyphenyl)-8-methyl-4-oxochromen-7-yl]oxyoxan-2-yl]methyl acetate
  参考文献：
  名称：

  O-Glycosidation reactions promoted by in situ generated silver N-heterocyclic carbenes in ionic liquids

  摘要：

  We herein report O-glycosidation reactions promoted via silver N-heterocyclic carbene complexes formed in situ in ionic liquids. Seven different room temperature ionic liquids were screened for the glycosidation reaction of 4-nitrophenol with tetra-O-acetyl-alpha-D-galactopyranosyl bromide. Good to excellent yields were obtained using Ag-NHC complexes derived from imidazolium halide salts to promote the glycosidation reaction, whereas yields considered moderate to low were obtained without use of the silver carbene complex. Anion metathesis of the ionic liquids with inexpensive alkylammonium halides also resulted in silver N-heterocyclic carbene formation and subsequent O-glycosidation in the presence of silver carbonate. Effective utility of this methodology has been demonstrated with biologically relevant acceptors (including flavones and steroids) where O-beta-glycoside products were obtained selectively in moderate to good yields. We have also demonstrated that the Ag-NHC complex is a superior promoter to traditionally used silver carbonate for the glycosidation of polyphenolic acceptors. The ionic liquids used in the study could be recycled three times without apparent loss in activity. (C) 2011 Published by Elsevier Ltd.

  DOI：

  10.1016/j.carres.2011.03.007

文献信息

• Application of silver N-heterocyclic carbene complexes in O-glycosidation reactions
  作者：Ian J. Talisman、Vineet Kumar、Jeffrey R. Deschamps、Mark Frisch、Sanjay V. Malhotra

  DOI：10.1016/j.carres.2011.07.025

  日期：2011.11

  We report the efficient O-glycosidation of glycosyl bromides with therapeutically relevant acceptors facilitated by silver N-heterocyclic carbene (Ag-NHC) complexes. A set of four Ag-NHC complexes was synthesized and evaluated as promoters for glycosidation reactions. Two new bis-Ag-NHC complexes derived from ionic liquids 1-benzyl-3-methyl-1H-imidazolium chloride and 1-(2-methoxyethyl)-3-methylimidazolium chloride were found to efficiently promote glycosidation, whereas known mono-Ag complexes of 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride and 1,3-bis(2,6-di-isopropylphenyl)imidazolium chloride failed to facilitate the reaction. The structures of the promoters were established by X-ray crystallography and these complexes were employed in the glycosidation of different glycosyl bromide donors with biologically valuable acceptors, such as estrone, estradiol, and various flavones. The products were obtained in yields considered good to excellent, and all reactions were highly selective for the 13 isomer regardless of neighboring group effects. (C) 2011 Elsevier Ltd. All rights reserved.