O-(2-deoxy-2-azido-3,4-di-O-benzyl-6-O-tert-butyldiphenylsilyl-α-D-galactopyranosyl) trichloroacetimidate | 1311399-46-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: O-(2-deoxy-2-azido-3,4-di-O-benzyl-6-O-tert-butyldiphenylsilyl-α-D-galactopyranosyl) trichloroacetimidate
• 英文别名: O-(2-azido-3,4-di-O-benzyl-6-O-tert-butyldiphenylsilyl-2-deoxy-α-D-galactopyranosyl) trichloroacetimidate；[(2R,3R,4R,5R,6R)-3-azido-6-[[tert-butyl(diphenyl)silyl]oxymethyl]-4,5-bis(phenylmethoxy)oxan-2-yl] 2,2,2-trichloroethanimidate
• CAS: 1311399-46-8
• 化学式: C₃₈H₄₁Cl₃N₄O₅Si
• 分子量: 768.212
• InChiKey: FFCOJTHUEKDHNH-CKQPALCZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.5
• 重原子数：
  51
• 可旋转键数：
  15
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  84.4
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  O-(2-deoxy-2-azido-3,4-di-O-benzyl-6-O-tert-butyldiphenylsilyl-α-D-galactopyranosyl) trichloroacetimidate 在 双(三甲基硫化硅) 、 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以73%的产率得到2-azido-3,4-di-O-benzyl-6-O-tert-butyldiphenylsilyl-2-deoxy-1-thio-α-D-galactopyranose
  参考文献：
  名称：

  Synthesis of Glycosylthiols and Reactivity Studies

  摘要：

  The acid-catalyzed reaction of 1,2-anhydro-3,4,6-tri-O-benzyl-alpha-D-glucopyranose (7) as glycosyl donor with bis-trimethylsilyl sulfide as acceptor affords the alpha-thiol. Hence, this sterically hindered S-nucleophile as acceptor should provide with O-glycosyl trichloroacetimidates as glycosyl donors that have nonparticipating groups at C-2, glycosylthiols with the thiol group in axial position. This was confirmed for various donors (4, 16-19) with the exception of the corresponding mannosyl donor (20). However, powerful participating groups at C-2 of the donor (23-28) governed the anomeric selectivity.

  DOI：

  10.1021/jo200624e
• 作为产物：
  描述：

  (2S,3R,4R,5R,6R)-3-azido-4,5-bis(benzyloxy)-6-(((tert-butyldiphenylsilyl)oxy)methyl)tetrahydro-2H-pyran-2-ol 、 三氯乙腈 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 以100%的产率得到O-(2-deoxy-2-azido-3,4-di-O-benzyl-6-O-tert-butyldiphenylsilyl-α-D-galactopyranosyl) trichloroacetimidate
  参考文献：
  名称：

  Synthesis of Glycosylthiols and Reactivity Studies

  摘要：

  The acid-catalyzed reaction of 1,2-anhydro-3,4,6-tri-O-benzyl-alpha-D-glucopyranose (7) as glycosyl donor with bis-trimethylsilyl sulfide as acceptor affords the alpha-thiol. Hence, this sterically hindered S-nucleophile as acceptor should provide with O-glycosyl trichloroacetimidates as glycosyl donors that have nonparticipating groups at C-2, glycosylthiols with the thiol group in axial position. This was confirmed for various donors (4, 16-19) with the exception of the corresponding mannosyl donor (20). However, powerful participating groups at C-2 of the donor (23-28) governed the anomeric selectivity.

  DOI：

  10.1021/jo200624e

文献信息

• Glycoside Bond Formation via Acid–Base Catalysis
  作者：Amit Kumar、Vipin Kumar、Ravindra T. Dere、Richard R. Schmidt

  DOI：10.1021/ol201231v

  日期：2011.7.15

  Acid–base catalyzed glycosyl donor and then glycosyl acceptor activation with phenylboron difluoride or diphenylboron fluoride permits hydrogen bond mediated intramolecular SN2-type glycosidation in generally high anomeric selectivity.

  酸碱催化的糖基供体，然后糖基受体激活与phenylboron氟或氟化物diphenylboron允许介导的分子内小号氢键Ñ在通常较高的异头选择性2型苷化。
• Synthesis of α-D-Gal<i>p</i>N₃-(1-3)-D-Gal<i>p</i>N₃: α- and 3-<i>O-</i>selectivity using 3,4-diol acceptors
  作者：Emil Glibstrup、Christian Marcus Pedersen

  DOI：10.3762/bjoc.14.258

  日期：——

  The motif α-D-GalpNAc-(1-3)-D-GalpNAc is very common in Nature and hence its synthesis highly relevant. The synthesis of its azido precursor has been studied and optimized in terms of steps, yields and selectivity. It has been found that glycosylation of the 3,4-diol acceptor is an advantage over the use of a 4-O-protected acceptor and that both regio- and anomeric selectivity is enhanced by bulky

  α-D-GalpNAc-（1-3）-D-GalpNAc基序在自然界很常见，因此其合成极为相关。已对其叠氮基前体的合成进行了步骤，产率和选择性方面的研究和优化。已经发现3，4-二醇受体的糖基化相对于使用4-O-保护的受体是有利的，并且庞大的6-O-保护基团提高了区域和异头异构体的选择性。受体和供体由共同的结构单元制成，限制了保护性操作，在这种情况下，不可避免的副反应。