(3aS,4R,5aR,9aR,9bS)-5-benzylidene-2,2,8,8-tetra-methylhexahydro-3aH-[1,3]dioxolo[4,5-h][1,3]benzodioxin-4-yl tert-butyl(dimethyl)silyl ether | 221044-99-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3aS,4R,5aR,9aR,9bS)-5-benzylidene-2,2,8,8-tetra-methylhexahydro-3aH-[1,3]dioxolo[4,5-h][1,3]benzodioxin-4-yl tert-butyl(dimethyl)silyl ether
• CAS: 221044-99-1
• 化学式: C₂₆H₄₀O₅Si
• 分子量: 460.686
• InChiKey: CNVJWUQPHBLYFC-BVAFDOMYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.76
• 重原子数：
  32.0
• 可旋转键数：
  3.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.69
• 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：

  (3aS,4R,5aR,9aR,9bS)-5-benzylidene-2,2,8,8-tetra-methylhexahydro-3aH-[1,3]dioxolo[4,5-h][1,3]benzodioxin-4-yl tert-butyl(dimethyl)silyl ether 在 四丁基氟化铵 、 四丁基碘化铵 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 生成 (3aR,4R,5aR,9aR,9bS)-5-benzylidene-4-(benzyloxy)-2,2,8,8-tetramethylhexahydro-3aH-[1,3]dioxolo[4,5-h][1,3]benzodioxine
  参考文献：
  名称：

  A novel entry to 5a-carba-hexopyranoses from carbohydrates based on a 6-exo-dig radical cyclization: synthesis of 5a-carba-β-d-mannopyranose pentaacetate

  摘要：

  来源于碳水化合物的2,3:4,6-二乙酰酮在C-1位置通过与苯乙炔反应进行 homologation，发生以C-5位置的自由基为中心的6-exo-dig自由基环化反应，生成与碳糖相关的高度功能化的环己烷。

  DOI：

  10.1039/a808848i
• 作为产物：
  描述：

  2,3:4,6-di-O-isopropylidene-D-mannopyranose 在 吡啶 、 4-二甲氨基吡啶 、 偶氮二异丁腈 、 三正丁基氢锡 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 、 乙腈 为溶剂， 反应 1.0h， 生成 (3aS,4R,5aR,9aR,9bS)-5-benzylidene-2,2,8,8-tetra-methylhexahydro-3aH-[1,3]dioxolo[4,5-h][1,3]benzodioxin-4-yl tert-butyl(dimethyl)silyl ether
  参考文献：
  名称：

  A novel entry to 5a-carba-hexopyranoses from carbohydrates based on a 6-exo-dig radical cyclization: synthesis of 5a-carba-β-d-mannopyranose pentaacetate

  摘要：

  来源于碳水化合物的2,3:4,6-二乙酰酮在C-1位置通过与苯乙炔反应进行 homologation，发生以C-5位置的自由基为中心的6-exo-dig自由基环化反应，生成与碳糖相关的高度功能化的环己烷。

  DOI：

  10.1039/a808848i

文献信息

• Stereodivergent Synthesis of Carbasugars from D-Mannose. Syntheses of 5a-Carba-α-D-allose, β-L-Talose, and α-L-Gulose Pentaacetates
  作者：Ana M. Gómez、Eduardo Moreno、Serafín Valverde、J. Cristóbal López

  DOI：10.1055/s-2002-31900

  日期：——

  A stereodivergent entry to 5a-carba-D- and L-pyranoses from a single precursor is described. The approach is based on the selective deoxygenation of polyoxygenated methylcyclohexane intermediates, readily available from radical cyclization of D-mannose derivatives. This strategy has been applied to the preparation of 5a-carba-α-D-allo-, 5a-carba-β-L-talo-, and 5a-carba-α-L-gulopyranose pentaacetates

  描述了从单一前体到 5a-carba-D-和 L-吡喃糖的立体发散进入。该方法基于多氧化甲基环己烷中间体的选择性脱氧，可从 D-甘露糖衍生物的自由基环化中轻松获得。该策略已应用于 5a-carba-α-D-allo-、5a-carba-β-L-talo-和 5a-carba-α-L-吡喃葡萄糖五乙酸酯的制备。
• Stereodivergent synthesis of 5a-carba-hexopyranoses from carbohydrates via 6-exo-dig radical cyclization: preparation of 5a-carba-β-d-manno-, α-d-allo-, β-l-talo- and α-l-gulopyranose pentaacetates from d-mannose
  作者：Ana M. Gómez、Eduardo Moreno、Gerardo O. Danelón、Serafı́n Valverde、J.Cristóbal López

  DOI：10.1016/s0957-4166(03)00532-9

  日期：2003.10

  Four carbasugars. 5a-carba-beta-D-manno-, alpha-D-allo-, beta-L-talo- and alpha-L-gulopyranose pentaacetates, have been prepared in a stereodivergent manner from D-mannose. Alkynyl derivatives of 2,3:4,6-di-O-isopropylidene-D-mannopyranose, which are prepared by homologation at C-1. by reaction with phenyl acetylide, undergo a 6-exo-dig radical cyclization, from a radical located at C-5. to yield a mixture of highly functionalized cyclohexanes. Some of these compounds, after transformation of their exocyclic double bond in a hydroxy function, were correlated with polyhydroxylated cyclohexanes, which were then selectively deoxygenated either at position C-4 or C-5a (carbohydrate numbering) to afford carbasugars of the D- Or L- series. (C) 2003 Elsevier Ltd. All rights reserved.