triethylsilyl 2-deoxy-2-((4-methoxyphenyl)-oxaziridin-2-yl)-3,4-bis-O-(triethylsilyl)-α-D-glucopyranoside | 1432490-97-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: triethylsilyl 2-deoxy-2-((4-methoxyphenyl)-oxaziridin-2-yl)-3,4-bis-O-(triethylsilyl)-α-D-glucopyranoside
• CAS: 1432490-97-5
• 化学式: C₃₂H₆₁NO₇Si₃
• 分子量: 656.095
• InChiKey: ZXHBVKGVQAJNRD-MROAMCDWSA-N

反应信息

• 作为反应物：
  描述：

  triethylsilyl 2-deoxy-2-((4-methoxyphenyl)-oxaziridin-2-yl)-3,4-bis-O-(triethylsilyl)-α-D-glucopyranoside 在 2,6-二甲基吡啶 、 三氟乙酸 、 三氯氧磷 作用下， 以 水 为溶剂， 生成 N-hydroxyglucosamine-6-phosphate
  参考文献：
  名称：

  Glucosamine and Glucosamine-6-phosphate Derivatives: Catalytic Cofactor Analogues for the glmS Ribozyme

  摘要：

  Two analogues of glucosamine-6-phosphate (GlcN6P, 1) and five of glucosamine (GlcN, 2) were prepared for evaluation as catalytic cofactors of the glmS ribozyme, a bacterial gene-regulatory RNA that controls cell wall biosynthesis. Glucosamine and allosamine with 3-azido substitutions were prepared by S(N)2 reactions of the respective 1,2,4,6-protected sugars; final acidic hydrolysis afforded the fully deprotected compounds as their TFA salts. A 6-phospho-2-aminoglucolactam (31) was prepared from glucosamine in a 13-step synthesis, which included a late-stage POCl3-phosphorylation. A simple and widely applicable 2-step procedure with the triethylsilyl (TES) protecting group was developed to selectively expose the 6-OH group in N-protected glucosamine analogues, which provided another route to chemical phosphorylation. Mitsunobu chemistry afforded 6-cyano (35) and 6-azido (36) analogues of GlcN-(Cbz), and the selectivity for the 6-position was confirmed by NMR (COSY, HMBC, HMQC) experiments. Compound 36 was converted to the fully deprotected 6-azido-GlcN (37) and 2,6-diaminoglucose (38) analogues. A 2-hydroxylamino glucose (42) analogue was prepared via an oxaziridine (41). Enzymatic phosphorylation of 42 and chemical phosphorylation of its 6-OH precursor (43) were possible, but 42 and the 6-phospho product (44) were unstable under neutral or basic conditions. Chemical phosphorylation of the previously described 2-guanidinyl-glucose (46) afforded its 6-phospho analogue (49) after final deprotection.

  DOI：

  10.1021/jo400192e
• 作为产物：
  描述：

  triethylsilyl 2-deoxy-2-((4-methoxyphenyl)-oxaziridin-2-yl)-3,4,6-tris-O-(triethylsilyl)-α-D-glucopyranoside 在 camphor-10-sulfonic acid 作用下， 以 甲醇 为溶剂， 反应 0.17h， 以18%的产率得到triethylsilyl 2-deoxy-2-((4-methoxyphenyl)-oxaziridin-2-yl)-3,4-bis-O-(triethylsilyl)-α-D-glucopyranoside
  参考文献：
  名称：

  Glucosamine and Glucosamine-6-phosphate Derivatives: Catalytic Cofactor Analogues for the glmS Ribozyme

  摘要：

  Two analogues of glucosamine-6-phosphate (GlcN6P, 1) and five of glucosamine (GlcN, 2) were prepared for evaluation as catalytic cofactors of the glmS ribozyme, a bacterial gene-regulatory RNA that controls cell wall biosynthesis. Glucosamine and allosamine with 3-azido substitutions were prepared by S(N)2 reactions of the respective 1,2,4,6-protected sugars; final acidic hydrolysis afforded the fully deprotected compounds as their TFA salts. A 6-phospho-2-aminoglucolactam (31) was prepared from glucosamine in a 13-step synthesis, which included a late-stage POCl3-phosphorylation. A simple and widely applicable 2-step procedure with the triethylsilyl (TES) protecting group was developed to selectively expose the 6-OH group in N-protected glucosamine analogues, which provided another route to chemical phosphorylation. Mitsunobu chemistry afforded 6-cyano (35) and 6-azido (36) analogues of GlcN-(Cbz), and the selectivity for the 6-position was confirmed by NMR (COSY, HMBC, HMQC) experiments. Compound 36 was converted to the fully deprotected 6-azido-GlcN (37) and 2,6-diaminoglucose (38) analogues. A 2-hydroxylamino glucose (42) analogue was prepared via an oxaziridine (41). Enzymatic phosphorylation of 42 and chemical phosphorylation of its 6-OH precursor (43) were possible, but 42 and the 6-phospho product (44) were unstable under neutral or basic conditions. Chemical phosphorylation of the previously described 2-guanidinyl-glucose (46) afforded its 6-phospho analogue (49) after final deprotection.

  DOI：

  10.1021/jo400192e