2-deoxy-2-iodo-3,4,6-tri-O-tert-butyldiphenylsilyl-β-D-glucopyranosyl acetate | 479352-40-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-deoxy-2-iodo-3,4,6-tri-O-tert-butyldiphenylsilyl-β-D-glucopyranosyl acetate
• 英文别名: 1-O-acetyl-2-deoxy-2-iodo-3,4,6-tri-O-tert-butyldiphenylsilyl-β-D-glucopyranose；TBDPS(-3)[TBDPS(-4)][TBDPS(-6)]b-Glc1Ac2I；[(2S,3R,4S,5R,6R)-4,5-bis[[tert-butyl(diphenyl)silyl]oxy]-6-[[tert-butyl(diphenyl)silyl]oxymethyl]-3-iodooxan-2-yl] acetate
• CAS: 479352-40-4
• 化学式: C₅₆H₆₇IO₆Si₃
• 分子量: 1047.31
• InChiKey: YMGWKOMKWLYCPK-XZRLMMIASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.55
• 重原子数：
  66
• 可旋转键数：
  18
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2-deoxy-2-iodo-3,4,6-tri-O-tert-butyldiphenylsilyl-β-D-glucopyranosyl acetate 在 咪唑 、 对甲苯磺酸 、 一水合肼 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 triethylamine tris(hydrogen fluoride) 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 24.0h， 生成 2-deoxy-2-iodo-3-O-tert-butyldimethylsilyl-4,6-O-benzylidene-β-D-glucopyranosyl trichloroacetimidate
  参考文献：
  名称：

  Concerning the Origin of the High β-Selectivity of Glycosidation Reactions of 2-Deoxy-2-iodo-glucopyranosyl Trichloroacetimidates

  摘要：

  [GRAPHICS]Studies on the glycosidation reactions of conformationally constrained glycosyl imidates 8a and 8b were performed to evaluate the possible involvement of "conformationally inverted" oxonium ion intermediates in glycosidation reactions with 2-deoxy-2-iodo-glucopyranosyl donors. The mechanistic implications of this study are discussed, and intermediates 23 and 24 are invoked to rationalize the observed beta-selectivities.

  DOI：

  10.1021/ol027066e
• 作为产物：
  描述：

  乙酰化葡萄烯糖 在 咪唑 、 N-碘代丁二酰亚胺 、 sodium methylate 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 12.17h， 生成 2-deoxy-2-iodo-3,4,6-tri-O-tert-butyldiphenylsilyl-β-D-glucopyranosyl acetate
  参考文献：
  名称：

  Concerning the Origin of the High β-Selectivity of Glycosidation Reactions of 2-Deoxy-2-iodo-glucopyranosyl Trichloroacetimidates

  摘要：

  [GRAPHICS]Studies on the glycosidation reactions of conformationally constrained glycosyl imidates 8a and 8b were performed to evaluate the possible involvement of "conformationally inverted" oxonium ion intermediates in glycosidation reactions with 2-deoxy-2-iodo-glucopyranosyl donors. The mechanistic implications of this study are discussed, and intermediates 23 and 24 are invoked to rationalize the observed beta-selectivities.

  DOI：

  10.1021/ol027066e

文献信息

• A New Procedure for Highly Regio‐ and Stereoselective Iodoacetoxylation of Protected Glycals and α‐1,2‐Cyclopropanated Sugars
  作者：David W. Gammon、Henok H. Kinfe、Dirk E. De Vos、Pierre A. Jacobs、Bert F. Sels

  DOI：10.1080/07328300701351524

  日期：2007.5.31

  less than 2 h at low temperatures to 2‐deoxy‐2‐iodoglycosyl acetates or novel 2‐deoxy‐2‐iodomethylglycosyl acetates using the simple, inexpensive reagent mixture of ammonium iodide, hydrogen peroxide, and acetic anhydride/acetic acid in acetonitrile. The protected glycals gave rise to 2‐deoxy‐2‐bromoglycosyl acetates when ammonium bromide was used instead of the iodide, although longer reaction times

  使用简单，廉价的方法，在低温下不到2小时的时间内，可以在不到2小时的时间内以高收率和高选择性将受保护的糖和α-1,2-环丙烷化的糖转化为2-脱氧-2-碘代糖基乙酸酯或新型2-脱氧-2-碘甲基糖基乙酸酯。碘化铵，过氧化氢和乙酸酐/乙酸在乙腈中的试剂混合物。当使用溴化铵代替碘化物时，尽管需要更长的反应时间并且选择性较差，但受保护的糖类会生成2-脱氧-2-溴代糖基乙酸酯。其他简单的烯烃，例如苯乙烯和茚，也被转化为它们相应的1,2-反-碘乙酸酯。
• Chemoenzymatic Synthesis of Uridine 5′-Diphospho-2-acetonyl-2-deoxy-α-<scp>d</scp>-glucose as C₂-Carbon Isostere of UDP-GlcNAc
  作者：Li Cai、Wanyi Guan、Wenlan Chen、Peng George Wang

  DOI：10.1021/jo100385p

  日期：2010.5.21

  2-ketoGlc, which is the C2-carbon isostere of GlcNAc, is a novel GlcNAc analogue with a ketone group. The corresponding glycosyltransferase donor substrate, UDP-2-ketoGlc, is necessary for synthesizing 2-ketoGlc-containing molecules and is thus highly important for metabolic polysaccharide remodeling and engineering. We report here the first chemoenzymatic synthesis of UDP-2-ketoGlc using our two-enzyme

  2-ketoGlc 是GlcNAc的 C 2 -碳等排体，是一种具有酮基的新型 GlcNAc 类似物。相应的糖基转移酶供体底物 UDP-2-ketoGlc 是合成含有 2-ketoGlc 的分子所必需的，因此对于代谢多糖重塑和工程非常重要。我们在这里报告了使用我们的双酶（NahK 和 GlmU）系统在体外首次化学酶法合成 UDP-2-ketoGlc。
• A simple, efficient alternative for highly stereoselective iodoacetoxylation of protected glycals
  作者：David W. Gammon、Henok H. Kinfe、Dirk E. De Vos、Pierre A. Jacobs、Bert F. Sels

  DOI：10.1016/j.tetlet.2004.10.166

  日期：2004.12

  yields and selectivities in less than 2 h at low temperatures to 2-deoxy-2-iodoglycosyl acetates using the simple, inexpensive reagent mixture of ammonium iodide, hydrogen peroxide and acetic anhydride/acetic acid in acetonitrile. The corresponding 2-deoxy-2-bromoglycosyl acetates are obtained using ammonium bromide instead of the iodide, although longer reaction times are required and selectivities are

  使用简单，廉价的碘化铵，过氧化氢和乙酸酐/乙酸在乙腈中的简单，廉价的试剂混合物，可以在低温下不到2小时的时间内，在不到2小时的时间内，高产率地将受保护的乙二醇转化为乙酸2-脱氧-2-碘代糖基乙酸酯。尽管需要更长的反应时间并且选择性差，但是使用溴化铵代替碘化物可获得相应的2-脱氧-2-溴糖基乙酸酯。