1,5-anhydro-1-iodo-4,6-(O-isopropylidene)-3-(O-triisopropylsilyl)-2-deoxy-D-arabino-hex-1-enitol | 1238373-63-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: 1,5-anhydro-1-iodo-4,6-(O-isopropylidene)-3-(O-triisopropylsilyl)-2-deoxy-D-arabino-hex-1-enitol
• 英文别名: (((4aR,8R,8aR)-6-iodo-2,2-dimethyl-4,4a,8,8a-tetrahydropyrano[3,2-d][1,3]dioxin-8-yl)oxy)triisopropylsilane
• CAS: 1238373-63-1
• 化学式: C₁₈H₃₃IO₄Si
• 分子量: 468.448
• InChiKey: LEMVZRFUUSHPNY-INMHGKMJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.37
• 重原子数：
  24.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  36.92
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  1,5-anhydro-1-iodo-4,6-(O-isopropylidene)-3-(O-triisopropylsilyl)-2-deoxy-D-arabino-hex-1-enitol 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以96%的产率得到1,5-anhydro-1-iodo-4,6-(O-isopropylidene)-2-deoxy-D-arabino-hex-1-enitol
  参考文献：
  名称：

  Total synthesis of (+)-papulacandin D

  摘要：

  A total synthesis of (+)-papulacandin D has been achieved in 31 steps, in a 9.2% overall yield from commercially available materials. The synthetic strategy divided the molecule into two nearly equal sized subunits, the spirocyclic C-arylglycopyranoside and the polyunsaturated fatty acid side-chain. The C-arylglycopyranoside was prepared in 11 steps in a 30% overall yield from triacetoxyglucal. The fatty acid side-chain was also prepared in 11 steps in a 30% overall yield from geraniol. The key strategic transformations in the synthesis are: (1) a palladium-catalyzed, organosilanolate-based cross-coupling reaction of a dimethylglucal-silanol with an electron-rich and sterically hindered aromatic iodide and (2) a Lewis-base catalyzed, enantioselective allylation reaction of a dienal and allyltrichlorosilane. A critical element in the successful execution of the synthesis was the development of a suitable protecting group strategy that satisfied a number of stringent criteria. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.03.093
• 作为产物：
  描述：

  1,5-anhydro-2-deoxy-3-O-triisopropylsilyl-4,6-O-isopropylidene-1-C-tributylstannyl-D-arabino-hex-1-enitol 在 碘 作用下， 以 二氯甲烷 为溶剂， 反应 0.08h， 生成 1,5-anhydro-1-iodo-4,6-(O-isopropylidene)-3-(O-triisopropylsilyl)-2-deoxy-D-arabino-hex-1-enitol
  参考文献：
  名称：

  Chiral Phosphoric Acid-Catalyzed Enantioselective and Diastereoselective Spiroketalizations

  摘要：

  Catalytic enantioselective and diastereoselective spiroketalizations with BINOL-derived chiral phosphoric acids are reported. The chiral catalyst can override the inherent preference for the formation of thermodynamic spiroketals, and highly selective formation of nonthermodynamic spiroketals could be achieved under the reaction conditions.

  DOI：

  10.1021/ja302704m

文献信息

• Photoredox Nickel‐Catalysed Stille Cross‐Coupling Reactions
  作者：Zhenghong Zhou、Jimin Yang、Bo Yang、Yang Han、Lijuan Zhu、Xiao‐Song Xue、Feng Zhu

  DOI：10.1002/anie.202314832

  日期：2023.12.21

  Stille reaction is designed for the first time, allowing for the construction of a rich range of C(sp3)−C(sp3), C(sp3)−C(sp2), and C(sp3)−C(sp) bonds in good to high yields with excellent stereoselectivity under exceptionally mild conditions. The innovative use of synergistic photoredox/nickel catalysis enables a novel single-electron transmetalation process of stannane reagents, providing a new research

  首次设计了一种新型光氧化还原/镍催化立体收敛Stille反应，可以构建丰富的C( sp 3 )−C( sp 3 )、C( sp 3 )−C( sp 2 )、 C( sp 3 )−C( sp ) 在极其温和的条件下以良好至高的产率以优异的立体选择性键合。协同光氧化还原/镍催化的创新应用实现了锡烷试剂的新型单电子金属转移过程，为 Stille 反应领域提供了新的研究范式。