((Z)-pent-2-en-1-yl)bis((1S,2R,3S,5S)-2,6,6-trimethylbicyclo[3.1.1]heptan-3-yl)borane | 887769-12-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: ((Z)-pent-2-en-1-yl)bis((1S,2R,3S,5S)-2,6,6-trimethylbicyclo[3.1.1]heptan-3-yl)borane
• CAS: 887769-12-2
• 化学式: C₂₅H₄₃B
• 分子量: 354.427
• InChiKey: YFDINKSZBQAJRT-OZENSNEJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.59
• 重原子数：
  26.0
• 可旋转键数：
  5.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  ((Z)-pent-2-en-1-yl)bis((1S,2R,3S,5S)-2,6,6-trimethylbicyclo[3.1.1]heptan-3-yl)borane 、 (E)-6-((tert-butyldimethylsilyl)oxy)-4-(2,2-dimethyl-6-((trimethylsilyl)ethynyl)-1,3-dioxan-4-yl)-4-((triethylsilyl)oxy)hex-2-enal 在 三氟化硼乙醚 、 双氧水 、 sodium hydroxide 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以2.23 g的产率得到(E)-9-((tert-butyldimethylsilyl)oxy)-7-(2,2-dimethyl-6-((trimethylsilyl)ethynyl)-1,3-dioxan-4-yl)-3-ethyl-7-((triethylsilyl)oxy)nona-1,5-dien-4-ol
  参考文献：
  名称：

  Formal Synthesis of Leustroducsin B via Reformatsky/Claisen Condensation of Silyl Glyoxylates

  摘要：

  A formal synthesis of leustroducsin B has been completed. The synthesis relies upon a recently developed Reformatsky/Claisen condensation of silyl glyoxylates and enantioenriched beta-lactones that establishes two of the molecule's three core stereocenters and permits further elaboration to an intermediate in Imanishl's synthesis via reliable chemistry (Prasad reduction, asymmetric pentenylation, Mitsunobu inversion).

  DOI：

  10.1021/ol2011192
• 作为产物：
  描述：

  (+)-二异松蒎烯基硼烷 在 正丁基锂 、 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 反应 4.41h， 生成 ((Z)-pent-2-en-1-yl)bis((1S,2R,3S,5S)-2,6,6-trimethylbicyclo[3.1.1]heptan-3-yl)borane
  参考文献：
  名称：

  Formal Synthesis of Leustroducsin B via Reformatsky/Claisen Condensation of Silyl Glyoxylates

  摘要：

  A formal synthesis of leustroducsin B has been completed. The synthesis relies upon a recently developed Reformatsky/Claisen condensation of silyl glyoxylates and enantioenriched beta-lactones that establishes two of the molecule's three core stereocenters and permits further elaboration to an intermediate in Imanishl's synthesis via reliable chemistry (Prasad reduction, asymmetric pentenylation, Mitsunobu inversion).

  DOI：

  10.1021/ol2011192

文献信息

• Asymmetric Pentenylation of Aldehydes: A New Benchmark for the Preparation of Ethyl-Substituted Homoallylic Alcohol
  作者：Stellios Arseniyadis、Janine Cossy、Ravindra Sonawane、Shyamsunder Joolakanti

  DOI：10.1055/s-0028-1087641

  日期：——

  A highly diastereo- and enantioselective boron-mediated pentenylation reaction is presented. The chiral pentenylborane ­reagents, which are derived from pinene, undergo addition to various aldehydes to afford ethyl-substituted homoallylic alcohols in good yield and high stereoselectivity. The latter are then easily converted into the corresponding α,β-unsaturated δ-lactones using an acylation/ring-closing metathesis sequence. The relative and absolute stereochemistry is exclusively controlled by the reagent.

  本文介绍了一种高度非对映选择性和对映选择性的硼介导戊烯化反应。从蒎烯衍生的手性戊烯基硼烷试剂与各种醛反应，以良好的产率和高度的立体选择性提供乙基取代的同烯丙基醇。后者随后通过酰化/环合复分解反应序列容易地转化为相应的α,β-不饱和δ-内酯。相对和绝对立体化学完全由试剂控制。