dimethyl 6-(triethylsiloxy)-2-oxohexylphosphonate | 1023950-31-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物
• 英文名称: dimethyl 6-(triethylsiloxy)-2-oxohexylphosphonate
• CAS: 1023950-31-3
• 化学式: C₁₄H₃₁O₅PSi
• 分子量: 338.456
• InChiKey: XBKXNSAWQDPXNQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.23
• 重原子数：
  21.0
• 可旋转键数：
  13.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  61.83
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  乙醇醛二聚体 、 dimethyl 6-(triethylsiloxy)-2-oxohexylphosphonate 在 N,N-二异丙基乙胺 、 lithium chloride 作用下， 以 乙腈 为溶剂， 生成 (E)-1-hydroxy-8-(triethylsilyloxy)oct-2-en-4-one
  参考文献：
  名称：

  Enantioselective, Organocatalytic Oxy-Michael Addition to γ/δ-Hydroxy-α,β-enones:  Boronate-Amine Complexes as Chiral Hydroxide Synthons

  摘要：

  An organocatalytic, enantioselective oxy-Michael addition to achiral gamma- and delta-hydroxy-alpha, beta-enones was developed. The key transformation is an unprecedented, asymmetric conjugate addition triggered by complexation between an in situ generated boronic acid hemiester and a chiral amine catalyst. Functionally, the intermediate amine-boronate complex acts as a chiral hydroxide surrogate or synthon. The resultant chiral beta-hydroxy-ketones are obtained in good to excellent yields and high ee following mild oxidative removal of the cyclic boronate. Natural products (R,12Z,15Z)-2-hydroxy-4-oxohenicosa-12,15-dienyl acetate and (+)-(S)-streptenol A were synthesized to demonstrate the utility of this reaction.

  DOI：

  10.1021/ja076802c

文献信息

• Titanium-Mediated Fragment Union Processes in Complex Molecule Synthesis: Development of a Branched Reaction Pathway of High Step Economy for the Synthesis of Complex and Diverse Polyketides
  作者：Glenn Micalizio、Lark Perez

  DOI：10.1055/s-2008-1032160

  日期：2008.2

  We describe a synthetic pathway to structurally complex and diverse polyketides based, in part, on regio- and stereoselective titanium-mediated coupling reactions. The sequences described allow for rapid assembly of polyketide-inspired architecture while providing significant flexibility for the establishment of diverse stereochemical relationships and substitution patterns along the carbon backbone (including stereodefined alkenes and 1,3-dienes, saturated and unsaturated lactones, hemiketals, α,β-unsaturated carbonyls, and spiroketals).

  我们描述了一条合成路径，用于合成结构复杂且多样的多酮类化合物，部分基于区位和立体选择性的钛介导耦合反应。所描述的合成序列允许快速组装多酮类启发的结构，同时在碳主链上建立多样的立体化学关系和取代模式（包括立体定义的烯烃和1,3-二烯、饱和和不饱和内酯、半缩醛、α,β-不饱和碳基化合物以及螺环醇）。