((3aR,5R,6S,6aR)-6-Benzyloxy-2,2-dimethyl-tetrahydro-furo[2,3-d][1,3]dioxol-5-ylmethoxy)-tert-butyl-diphenyl-silane | 213963-74-7

• 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: ((3aR,5R,6S,6aR)-6-Benzyloxy-2,2-dimethyl-tetrahydro-furo[2,3-d][1,3]dioxol-5-ylmethoxy)-tert-butyl-diphenyl-silane
• CAS: 213963-74-7
• 化学式: C₃₁H₃₈O₅Si
• 分子量: 518.725
• InChiKey: UZXHFYRUZCBWLR-VJLHXPKFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.02
• 重原子数：
  37.0
• 可旋转键数：
  8.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  46.15
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  ((3aR,5R,6S,6aR)-6-Benzyloxy-2,2-dimethyl-tetrahydro-furo[2,3-d][1,3]dioxol-5-ylmethoxy)-tert-butyl-diphenyl-silane 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 以81%的产率得到3-O-benzyl-1,2-O-isopropylidene-α-D-xylofuranose
  参考文献：
  名称：

  Convenient conversion of wheat hemicelluloses pentoses (d-xylose and l-arabinose) into a common intermediate

  摘要：

  The transformation Of D-xylose and L-arabinose, the two major components of wheat straw and bran, into a unique multifunctional, optically pure, five-carbon synthon has been achieved. The synthetic sequence requires three steps: suitable protection of the hydroxyl groups of the pentoses, introduction of an iodide at the C-5 position and zinc-mediated opening of the furanose ring leading to the formation of a common substituted pent-4-enal. (C) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2007.07.010
• 作为产物：
  描述：

  1,2-O-(异丙亚基)-5-O-(三苯基甲基)-alpha-D-呋喃木糖 在 咪唑 、 四丁基氟化铵 、 sodium hydride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 paraffin 为溶剂， 反应 39.0h， 生成 ((3aR,5R,6S,6aR)-6-Benzyloxy-2,2-dimethyl-tetrahydro-furo[2,3-d][1,3]dioxol-5-ylmethoxy)-tert-butyl-diphenyl-silane
  参考文献：
  名称：

  Two novel synthetic methods for 1,4-anhydro-α-d-xylopyranose derivatives

  摘要：

  Two novel methods for the syntheses of 1,4-anhydro-3-O-benzyl-2-O-pivaloyl- (1) and 2-O-acetyl-1,4-anhydro-3-O-benzyl-alpha-D-xylopyranose (2), starting materials for synthesizing stereoregular beta-(1-->5)-xylofuranan by ring-opening polymerization are reported. Both synthetic routes start from D-xylopyranose, involve nine reaction steps, and give approximately 30-35% overall yields. The key reaction in the novel synthetic routes is the intramolecular nucleophilic attack of C-1 oxyanion on the C-5 position of 3-O-benzyl-5-O-(p-toluenesulfonyl)-alpha-D-xylofuranose (10), resulting in 1,5-acetal bond formation in high yield. The present synthetic routes enable us to prepare 1,4-anhydro-alpha-D-xylopyranose derivatives having different substituents at the 2-O- and the 3-O-positions. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(98)00135-9

文献信息

• Analysis of UDP-<scp>d</scp>-Apiose/UDP-<scp>d</scp>-Xylose Synthase-Catalyzed Conversion of UDP-<scp>d</scp>-Apiose Phosphonate to UDP-<scp>d</scp>-Xylose Phosphonate: Implications for a Retroaldol–Aldol Mechanism
  作者：Sei-hyun Choi、Steven O. Mansoorabadi、Yung-nan Liu、Tun-Cheng Chien、Hung-wen Liu

  DOI：10.1021/ja305322x

  日期：2012.8.29

  UDP-D-apiose/UDP-D-xylose synthase (AXS) catalyzes the conversion of UDP-D-glucuronic acid to UDP-D-apiose and UDP-D-xylose. An acetyl-protected phosphonate analogue of UDP-D-apiose was synthesized and used in an in situ HPLC assay to demonstrate for the first time the ability of AXS to interconvert the two reaction products. Density functional theory calculations provided insight into the energetics of this process and the apparent inability of AXS to catalyze the conversion of UDP-D-xylose to UDP-D-apiose. The data suggest that this observation is unlikely to be due to an unfavorable equilibrium but rather results from substrate inhibition by the most stable chair conformation of UDP-D-xylose. The detection of xylose cyclic phosphonate as the turnover product reveals significant new details about the AXS-catalyzed reaction and supports the proposed retroaldol-aldol mechanism of catalysis.