phenyl 6-deoxy-2,3,4-tri-O-tert-butyldimethylsilyl-1-thio-α-L-mannopyranoside | 947256-89-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 6-deoxy-2,3,4-tri-O-tert-butyldimethylsilyl-1-thio-α-L-mannopyranoside
• 英文别名: TBDMS(-2)[TBDMS(-3)][TBDMS(-4)]Rha(a)-SPh；[(2S,3S,4R,5R,6S)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-methyl-6-phenylsulfanyloxan-4-yl]oxy-tert-butyl-dimethylsilane
• CAS: 947256-89-5
• 化学式: C₃₀H₅₈O₄SSi₃
• 分子量: 599.111
• InChiKey: LRXSSXGIKHZCEO-KFRGZICISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.69
• 重原子数：
  38
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  62.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  phenyl 6-deoxy-2,3,4-tri-O-tert-butyldimethylsilyl-1-thio-α-L-mannopyranoside 在 N-碘代丁二酰亚胺 、 四丁基氟化铵 、 silver trifluoromethanesulfonate 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 5.0h， 生成
  参考文献：
  名称：

  Isoprenoid Phosphonophosphates as Glycosyltransferase Acceptor Substrates

  摘要：

  Glycosyltransferases that act on polyprenol pyrophosphate substrates are challenging to study because their lipid-linked substrates are difficult to isolate from natural sources and arduous to synthesize. To facilitate access to glycosyl acceptors, we assembled phosphonophosphate analogues and showed these are effective substrate surrogates for GlfT1, the essential product of mycobacterial gene Rv3782. Under chemically defined conditions, the galactofuranosyltransferase GlfT1 catalyzes the formation of a tetrasaccharide sequence en route to assembly of the mycobacterial galactan.

  DOI：

  10.1021/ja500622v
• 作为产物：
  描述：

  叔丁基二甲硅基三氟甲磺酸酯 、 phenyl 1-thio-α-L-rhamnopyranose 在 吡啶 、 4-二甲氨基吡啶 作用下， 以99%的产率得到phenyl 6-deoxy-2,3,4-tri-O-tert-butyldimethylsilyl-1-thio-α-L-mannopyranoside
  参考文献：
  名称：

  “Super Armed” Glycosyl Donors:  Conformational Arming of Thioglycosides by Silylation

  摘要：

  Glycosyl donors protected with bulky silyl protective groups (tert-butyldimethylsilyl, TBS), on the 2-, 3-, and 4-OH groups were found to have superior reactivity compared with benzylated thioglucosides. The enhanced reactivity is explained by the stereoelectronic effects associated with the conformational change induced by the silylation. A TBS silylated thioglucoside donor has axial OR groups, whereas a benzylated thioglucoside has equatorial OR groups, leading to much more favorable charge-dipole interactions in the transition state. This concept could be used to create "super armed" glucosyl, mannosyl, rhamnosyl, and galactosyl donors, which could cross-couple with the armed acceptors, phenyl 2,3,4-tri-O- benzyl-beta-D-thioglucoside or phenyl 2,3,6-tri-O-benzyl-beta-D-thioglucoside, to give the corresponding armed disaccharides in good to excellent yields.

  DOI：

  10.1021/ja071955l

文献信息

• Conformationally armed glycosyl donors: reactivity quantification, new donors and one pot reactions
  作者：Christian Marcus Pedersen、Lavinia G. Marinescu、Mikael Bols

  DOI：10.1039/b801305e

  日期：——

  The relative reactivity of conformationally armed thioglycosides is quantified.

  相对反应性被量化为构象性活化的硫代糖苷。
• “Super Armed” Glycosyl Donors:  Conformational Arming of Thioglycosides by Silylation
  作者：Christian Marcus Pedersen、Lars Ulrik Nordstrøm、Mikael Bols

  DOI：10.1021/ja071955l

  日期：2007.7.1

  Glycosyl donors protected with bulky silyl protective groups (tert-butyldimethylsilyl, TBS), on the 2-, 3-, and 4-OH groups were found to have superior reactivity compared with benzylated thioglucosides. The enhanced reactivity is explained by the stereoelectronic effects associated with the conformational change induced by the silylation. A TBS silylated thioglucoside donor has axial OR groups, whereas a benzylated thioglucoside has equatorial OR groups, leading to much more favorable charge-dipole interactions in the transition state. This concept could be used to create "super armed" glucosyl, mannosyl, rhamnosyl, and galactosyl donors, which could cross-couple with the armed acceptors, phenyl 2,3,4-tri-O- benzyl-beta-D-thioglucoside or phenyl 2,3,6-tri-O-benzyl-beta-D-thioglucoside, to give the corresponding armed disaccharides in good to excellent yields.
• Isoprenoid Phosphonophosphates as Glycosyltransferase Acceptor Substrates
  作者：Mario A. Martinez Farias、Virginia A. Kincaid、Venkatachalam R. Annamalai、Laura L. Kiessling

  DOI：10.1021/ja500622v

  日期：2014.6.18

  Glycosyltransferases that act on polyprenol pyrophosphate substrates are challenging to study because their lipid-linked substrates are difficult to isolate from natural sources and arduous to synthesize. To facilitate access to glycosyl acceptors, we assembled phosphonophosphate analogues and showed these are effective substrate surrogates for GlfT1, the essential product of mycobacterial gene Rv3782. Under chemically defined conditions, the galactofuranosyltransferase GlfT1 catalyzes the formation of a tetrasaccharide sequence en route to assembly of the mycobacterial galactan.