t-butyldiphenylsilyl 2-azido-3,6-di-O-benzyl-2-deoxy-β-D-dlucopyranoside | 144914-16-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: t-butyldiphenylsilyl 2-azido-3,6-di-O-benzyl-2-deoxy-β-D-dlucopyranoside
• 英文别名: tert-butyldiphenylsilyl 2-azido-3,6-di-O-benzyl-2-deoxy-β-D-dlucopyranoside；tert-butyldiphenylsilyl-2-azido-2-deoxy-3,6-di-O-benzyl-β-D-glucopyranose；(2R,3S,4R,5R,6S)-5-azido-6-[tert-butyl(diphenyl)silyl]oxy-4-phenylmethoxy-2-(phenylmethoxymethyl)oxan-3-ol
• CAS: 144914-16-9
• 化学式: C₃₆H₄₁N₃O₅Si
• 分子量: 623.824
• InChiKey: XZKFHXNCJJAYPZ-JSMUHSIHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.13
• 重原子数：
  45
• 可旋转键数：
  13
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  71.5
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  t-butyldiphenylsilyl 2-azido-3,6-di-O-benzyl-2-deoxy-β-D-dlucopyranoside 在 溶剂黄146 、 锌 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 生成
  参考文献：
  名称：

  Stereoselective synthesis of benzyl-protected β-galactosides by propionitrile-mediated glycosylation

  摘要：

  beta-Selective galactosylation was studied using a series of 2-O-benzylated phenyl 1-thio-galactosides and glycosyl acceptors in propionitrile with BSP-TTBP-Tf2O. The glycosylation enabled us to synthesize useful precursors of N-acetyllactosamine and core 1 O-glycoserine derivatives in a highly convergent manner. (c) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2008.01.029
• 作为产物：
  描述：

  tert-butyldiphenylsilyl 2-azido-2-dedeoxy-3-O-benzylidene-β-D-glucopyranoside 在 4 A molecular sieve 、 sodium cyanoborohydride 作用下， 以 四氢呋喃 为溶剂， 以97%的产率得到t-butyldiphenylsilyl 2-azido-3,6-di-O-benzyl-2-deoxy-β-D-dlucopyranoside
  参考文献：
  名称：

  An efficient access to protected disialylated glycohexaosyl threonine present on the leukosialin of activated T-lymphocytes

  摘要：

  The total synthesis of the threonine-linked core 2 class disialylated hexasaccharide in a completely protected form was accomplished for the first time. The L-threonine conjugate, N-(9-fluorenylmethoxycarbonyl)-O-{(5-acetomido-4,7,8,9-tetra-O-benzyl-3,5-dideoxy-D-glycero-alpha-D-galacto-2-nonulopyranosylanic acid)-(2 --> 3)-(2,6-di-O-benzyl-beta-D-galactopyranosyl)-(1 --> 4)-2-acetamido-2-deoxy-3,6-di-O-benzyl-beta-D-glucopyranosyl-(1 --> 6)-[(5-acctamido-4,7,8,9-tetra-O-benzyl-3, 5-dideoxy-D-glycero-alpha-D-galacto-2-nonulopyranosylonic acid)-(2 --> 3)-2,6-di-O-benzyl-beta-D-galactopyranosyl-(1 --> 3)]-2-acetamido-2-deoxy-alpha-D-galactopyranosyl-(1d --> 4c:1f --> 4e)-dilactone}-L-threonine allyl ester was synthesized via stereocontrolled glycosylations employing readily accessible monosaccharidic blocks; t-butyl-diphenylsilyl-2-azido-2-deoxy-3, 6-di-O-benzyl-beta-D-glucopyranose, N-(9-fluorenylmethoxycarbonyl)-O-(2-azir-butylditnethylsilyl-2-deoxy-alpha-D-galactopyranosyl)-L-threonine allyl ester, 8, 9 and N-(9-fluorenylmethoxycarbonyl)-O-(2-azido-4,6-O-benzylidene-3-O-chloroacetyl-2-deoxy-alpha-D-galactopyranosy;)-L-threonine allyl ester. For the introduction of the amino acid. the azide group was used to temporarily mask the amino group of GalNAc so as to obtain an alpha-glycosidic linkage without participation from the C-2 substituent. The threonine was attached to the sugar unit at the monosaccharide stage to avoid loss of oligosaccharide at a later stage. The Fmoc and allyl ester protected amino acid at the reducing end facilitates efficient glycopeptide synthesis on solid-phase support. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(99)00313-4

文献信息

• Solid-phase synthesis of core 2 O-linked glycopeptide and its enzymatic sialylation
  作者：Yutaka Takano、Naoya Kojima、Yuko Nakahara、Hironobu Hojo、Yoshiaki Nakahara

  DOI：10.1016/j.tet.2003.08.047

  日期：2003.10

  tetrasaccharide building blocks (1a/1b) for solid-phase synthesis of glycopeptide were synthesized via stereoselective glycosylation of the disaccharyl Ser/Thr (3a/3b) with a glycosyl fluoride (2) carrying the 2-trichloroacetamido group that was readily converted into a 2-acetamido group by reduction. A segment of glycoprotein leukosialin (215–224) was synthesized by the solid-phase protocol, the building block (1b)

  固相合成糖肽的核心2型四糖结构单元（1a / 1b）是通过二糖基Ser / Thr（3a / 3b）与带有2-三氯乙酰胺基的糖基氟化物（2）的立体选择性糖基化合成的。通过还原容易地将其转化为2-乙酰氨基基团。固相规程合成了糖蛋白白蜡蛋白（215-224）的一个片段，即构件（1b）被利用。用试剂K从树脂上切割合成糖肽，然后用“低酸度TfOH”混合物对产物进行处理，促进了苄基的完全除去，糖苷键的损失最小。通过使用特定的唾液酸转移酶，以非常高的效率将N-乙酰神经氨酸（唾液酸）残基酶促地引入到去保护的糖肽（21）中。
• Preparation of core 2 type tetrasaccharide carrying decapeptide by benzyl protection-based solid-phase synthesis strategy
  作者：Yutaka Takano、Motoki Habiro、Masaomi Someya、Hironobu Hojo、Yoshiaki Nakahara

  DOI：10.1016/s0040-4039(02)01947-0

  日期：2002.11

  alNAc-(1→3)-l-Ser/Thr building blocks for solid-phase synthesis of glycopeptide were stereoselectively synthesized in a benzyl-protected form. The key glycosylation reaction to form β-d-GlcNAc linkage was established by the use of protected N-trichloroacetyl-d-lactosaminyl fluoride. Usefulness of the building block was demonstrated by solid-phase synthesis of a segment of human leukosialin. Benzyl

  β-d-Gal-（1→4）-β-d-GlcNAc-[β-d-Gal-（1→3）]-α-d-GalNAc-（1→3）-l-Ser / Thr构建以苄基保护的形式立体选择性地合成糖肽的固相合成嵌段。形成β-d-GlcNAc键的关键糖基化反应是通过使用受保护的N-三氯乙酰基-d-乳糖胺基氟化物建立的。该构建基的有用性通过人类白细胞唾液酸蛋白片段的固相合成证明。通过“低酸度TfOH”条件可有效去除苄基保护基。
• The first total synthesis of the core class II disialylated hexasaccharide as a building block for glycopeptide synthesis
  作者：Latika Singh、Yuko Nakahara、Yukishige Ito、Yoshiaki Nakahara

  DOI：10.1016/s0040-4039(99)00605-x

  日期：1999.5

  The first total synthesis of the protected core class II sialylated glycosyl-Thr hexasaccharide (3), utilizing suitably protected building blocks 4, 5, 7 and 8 was accomplished. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Stereoselective synthesis of benzyl-protected β-galactosides by propionitrile-mediated glycosylation
  作者：Akiharu Ueki、Masafumi Hirota、Yuta Kobayashi、Keiko Komatsu、Yutaka Takano、Michio Iwaoka、Yuko Nakahara、Hironobu Hojo、Yoshiaki Nakahara

  DOI：10.1016/j.tet.2008.01.029

  日期：2008.3

  beta-Selective galactosylation was studied using a series of 2-O-benzylated phenyl 1-thio-galactosides and glycosyl acceptors in propionitrile with BSP-TTBP-Tf2O. The glycosylation enabled us to synthesize useful precursors of N-acetyllactosamine and core 1 O-glycoserine derivatives in a highly convergent manner. (c) 2008 Elsevier Ltd. All rights reserved.
• An efficient access to protected disialylated glycohexaosyl threonine present on the leukosialin of activated T-lymphocytes
  作者：Latika Singh、Yuko Nakahara、Yukishige Ito、Yoshiaki Nakahara

  DOI：10.1016/s0008-6215(99)00313-4

  日期：2000.4

  The total synthesis of the threonine-linked core 2 class disialylated hexasaccharide in a completely protected form was accomplished for the first time. The L-threonine conjugate, N-(9-fluorenylmethoxycarbonyl)-O-(5-acetomido-4,7,8,9-tetra-O-benzyl-3,5-dideoxy-D-glycero-alpha-D-galacto-2-nonulopyranosylanic acid)-(2 --> 3)-(2,6-di-O-benzyl-beta-D-galactopyranosyl)-(1 --> 4)-2-acetamido-2-deoxy-3,6-di-O-benzyl-beta-D-glucopyranosyl-(1 --> 6)-[(5-acctamido-4,7,8,9-tetra-O-benzyl-3, 5-dideoxy-D-glycero-alpha-D-galacto-2-nonulopyranosylonic acid)-(2 --> 3)-2,6-di-O-benzyl-beta-D-galactopyranosyl-(1 --> 3)]-2-acetamido-2-deoxy-alpha-D-galactopyranosyl-(1d --> 4c:1f --> 4e)-dilactone}-L-threonine allyl ester was synthesized via stereocontrolled glycosylations employing readily accessible monosaccharidic blocks; t-butyl-diphenylsilyl-2-azido-2-deoxy-3, 6-di-O-benzyl-beta-D-glucopyranose, N-(9-fluorenylmethoxycarbonyl)-O-(2-azir-butylditnethylsilyl-2-deoxy-alpha-D-galactopyranosyl)-L-threonine allyl ester, 8, 9 and N-(9-fluorenylmethoxycarbonyl)-O-(2-azido-4,6-O-benzylidene-3-O-chloroacetyl-2-deoxy-alpha-D-galactopyranosy;)-L-threonine allyl ester. For the introduction of the amino acid. the azide group was used to temporarily mask the amino group of GalNAc so as to obtain an alpha-glycosidic linkage without participation from the C-2 substituent. The threonine was attached to the sugar unit at the monosaccharide stage to avoid loss of oligosaccharide at a later stage. The Fmoc and allyl ester protected amino acid at the reducing end facilitates efficient glycopeptide synthesis on solid-phase support. (C) 2000 Elsevier Science Ltd. All rights reserved.