phenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-allopyranoside | 927420-46-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-allopyranoside
• 英文别名: (2R,3R,4R,5R,6S)-3,4,5-tris(phenylmethoxy)-2-(phenylmethoxymethyl)-6-phenylsulfanyloxane
• CAS: 927420-46-0
• 化学式: C₄₀H₄₀O₅S
• 分子量: 632.821
• InChiKey: IKCMSYGNAFDJNX-VTDZCKIGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.9
• 重原子数：
  46
• 可旋转键数：
  15
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  71.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  phenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-allopyranoside 在 N-溴代丁二酰亚胺(NBS) 、 水 、 calcium carbonate 作用下， 以 乙腈 为溶剂， 反应 3.0h， 以73%的产率得到(2R,3R,4R,5R,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-ol
  参考文献：
  名称：

  WO2007/25043

  摘要：

  公开号：
• 作为产物：
  描述：

  phenyl 1-thio-β-D-allopyranoside 、 溴甲苯 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以72%的产率得到phenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-allopyranoside
  参考文献：
  名称：

  Stereodirecting Effect of the Pyranosyl C-5 Substituent in Glycosylation Reactions

  摘要：

  The stereodirecting effect of the glycosyl C-5 substituent has been investigated in a series of D-pyranosyl thioglycoside donors and related to their preferred positions in the intermediate H-3(4) and H-4(3) half-chair oxacarbenium ions. Computational studies showed that an axially positioned C-5 carboxylate ester can stabilize the (3)H4 half-chair oxacarbenium ion conformer by donating electron densit from its carbonyl function into the electron-poor oxacarbenium ion functionality. A similar stabilization can be achieved by a C-5 benzyloxyrnethyl group, but,the magnitude of this stabilization is significantly smaller than for the C-5 carboxylate ester. As a result, the preference of the C-5 benzyloxymethyl to occupy an axial position in the half-chair oxacarbenium ions is much reduced compared to the C-5 carboxylate ester. To minimize steric interactions, a C-5 methyl group prefers to adopt an equatorial position and therefore favors the H-4(3) half-chair oxacarbenium ion. When all pyranosyl substituents occupy their favored position in one of the two intermediate half-chair oxacarbenium ions, highly stereoselective glycosylations can be achieved as revealed by the excellent beta-selectivity of mannuronate esters and alpha-selectivity of 6-deoxygulosides.

  DOI：

  10.1021/jo900662v

文献信息

• Seven-membered ring nucleosides
  申请人：Storer Richard

  公开号：US20070185063A1

  公开（公告）日：2007-08-09

  The present invention provides nucleoside analogue compounds that treat a host infected with a Flaviviridae virus infection, or other viruses that exhibit RNA-dependent RNA viral replication, compositions comprising these compounds and methods of using the compounds for the treatment and/or prophylaxis of viral infection, especially hepatitis C, in an infected host.
• WO2007/25043
  申请人：——

  公开号：——

  公开（公告）日：——
• Stereodirecting Effect of the Pyranosyl C-5 Substituent in Glycosylation Reactions
  作者：Jasper Dinkelaar、Ana Rae de Jong、Robert van Meer、Mark Somers、Gerrit Lodder、Herman S. Overkleeft、Jeroen D. C. Codée、Gijsbert A. van der Marel

  DOI：10.1021/jo900662v

  日期：2009.7.17

  The stereodirecting effect of the glycosyl C-5 substituent has been investigated in a series of D-pyranosyl thioglycoside donors and related to their preferred positions in the intermediate H-3(4) and H-4(3) half-chair oxacarbenium ions. Computational studies showed that an axially positioned C-5 carboxylate ester can stabilize the (3)H4 half-chair oxacarbenium ion conformer by donating electron densit from its carbonyl function into the electron-poor oxacarbenium ion functionality. A similar stabilization can be achieved by a C-5 benzyloxyrnethyl group, but,the magnitude of this stabilization is significantly smaller than for the C-5 carboxylate ester. As a result, the preference of the C-5 benzyloxymethyl to occupy an axial position in the half-chair oxacarbenium ions is much reduced compared to the C-5 carboxylate ester. To minimize steric interactions, a C-5 methyl group prefers to adopt an equatorial position and therefore favors the H-4(3) half-chair oxacarbenium ion. When all pyranosyl substituents occupy their favored position in one of the two intermediate half-chair oxacarbenium ions, highly stereoselective glycosylations can be achieved as revealed by the excellent beta-selectivity of mannuronate esters and alpha-selectivity of 6-deoxygulosides.